TWI656097B - Surface modified silica particles and polyimide film comprising the same - Google Patents

Abstract

The invention discloses a surface-modified cerium oxide particle and a polyimide film containing the cerium oxide particle, wherein the modified cerium oxide particle is modified by a phenyl group-containing polyoxy siloxane. Further, the compatibility and dispersibility of the polymer are improved, and the polymer composite having excellent surface strength characteristics, in particular, a polyimide film, is obtained by using the modified ceria particles.

Description

Surface modified cerium oxide particles and polyimide film containing the cerium oxide particles

The present invention relates to a surface-modified cerium oxide particle and a polyimide film containing the cerium oxide particle, and more particularly to a surface-modified cerium oxide particle and a polymer as an organic substance The compatibility and dispersibility are maximized, and an organic-inorganic composite polyimine film containing the cerium oxide particles.

In general, polyimine (PI) resin is an extremely high heat resistant resin which is insoluble and insoluble, and has excellent heat oxidation resistance, heat resistance, radiation resistance, low temperature characteristics, and drug resistance characteristics, and is widely used in automobiles. Heat-resistant cutting-edge materials such as materials, aerospace materials, and spacecraft materials, and insulating coating agents, insulating films, semiconductors, and electrode protective films for TFT-LCDs.

In the case of such a polyimine, a polyphthalamide derivative is usually obtained by solution polymerization of an aromatic dianhydride and an aromatic diamine or an aromatic diisocyanate, and then subjected to ring closure dehydration at a high temperature. It is obtained by carrying out hydrazine imidization. In order to prepare a polyimine resin, pyromellitic acid (PMDA) or biphenyltetracarboxylic dianhydride (BPDA) or the like is used as an aromatic dianhydride component, and oxydianiline (ODA) or p-phenylenediamine (p) is used. - PDA), m-phenylenediamine (m-PDA), methylene diamine (MDA), bisaminophenyl hexafluoropropane (HFDA) as an aromatic diamine component.

In general, polyimine is colored brown or yellow due to a high density of aromatic rings, and transparency is imparted to brown and yellow polyimine in order to be used in a tip field such as a display or a semiconductor. To this end, by introducing a linkage group (-O-, -SO ₂ -, -CO-, -CF ₃ CCF ₃ -, etc.) or a side chain having a relatively large free volume into the main chain, Transparency is achieved by minimizing intermolecular or intramolecular charge transfer complexes.

However, a polyimide film is provided with a transparency, and the heat resistance is lowered due to the introduced functional group. Therefore, there is a limit in the use in the field of material processes such as displays requiring high process temperatures. Further, in the case where the mechanical physical properties are low, tearing occurs in the preparation process of the display, resulting in a decrease in product yield.

In order to overcome the disadvantages of such a transparent polyimide film, other forms of non-polymer materials may be contained, and a representative example thereof may be a Si series inorganic substance. In the case of producing a film, in the case where such a filler formed of an inorganic substance is contained, the runnability can be improved, or the hardness, the deformation of the optical physical property, and the heat resistance can be enhanced as needed.

The prior art of the technique of introducing cerium oxide into the polyimine is exemplified by the Korean Patent No. 0652863, which discloses "cerium oxide-polyimine mixture and its preparation method", and discloses "poly" Precursor solution for imine/ceria composite, preparation method thereof, and polyamidene/ceria composite material having low volume shrinkage, Korean Patent No. 1246116, and "Polya" International Published Patent WO2005-080505 and the like of the amine alkane solution composition.

However, in the case of most inorganic substances, when the amount of use is large, although there are some differences depending on the size of the particles and the preparation method of the particles, when the film is formed, the aggregation of the inorganic substances may occur. A critical point at which the haze becomes high is displayed. Further, the inorganic substance itself has poor compatibility with the polymer, resulting in a decrease in dispersibility. In order to prevent this problem, dispersion is performed by a physical method such as a mill, a mixer, a high-speed mixer, a homogenizer, and an ultrasonic disperser. Therefore, there is an urgent need to develop a technique capable of further improving the compatibility with a polymer.

An object of the present invention is to improve the compatibility and dispersibility of an inorganic polymer by modifying the surface of the cerium oxide particles, and further improve the inclusion of the surface-modified cerium oxide particles. The heat resistance, transparency and surface hardness of the polyimide film.

In a specific embodiment of the present invention, there is provided a surface-modified cerium oxide, wherein the surface-modified cerium oxide is cerium oxide particles modified by a polyoxyalkylene oxide on the surface, and the polyoxyalkylene oxide is a polymer of a single compound represented by the following Chemical Formula 1, a polymer of a mixture of a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2, and a phenyl group in a side chain;

In the above Chemical Formula 1 or Chemical Formula 2, R is one selected from the group consisting of H, a halogen atom, an alkoxy group having 1 to 6 carbon atoms substituted or unsubstituted by a halogen atom, and a combination thereof, and each R may be the same as each other. Or different. Further, R ₁ is a single bond in which a carbon selected from a benzene ring is directly bonded to an anthracene, an alkylene group having 1 to 8 carbon atoms, and an alkenyl group having 3 to 12 carbon atoms (alkenylene). Group), one of a halogenated alkenyl group having 3 to 12 carbon atoms, an alkynylene group having 3 to 8 carbon atoms, and a combination thereof.

In a preferred embodiment, the polyoxyalkylene oxide may be a polymer obtained by mixing a compound represented by the above Chemical Formula 1 with a compound represented by the above Chemical Formula 2 in a weight ratio of 1:1 to 1:5. .

The above polyoxyalkylene oxide in a specific example of the present invention may have a weight average molecular weight of 1,000 to 10,000.

The surface-modified ceria having a specific surface in one specific example of the present invention may have an average particle diameter of 0.1 to 50 μm.

In a specific example of the present invention, the polypyrone may be contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the cerium oxide particles.

In another embodiment of the present invention, a polyimide film is provided, wherein the polyimide film contains a polyimide resin and cerium oxide particles; and the cerium oxide particles are surface-treated with polyoxyalkylene oxide. The modified cerium oxide particles; the polyoxy siloxane is a polymer of a single compound represented by the following Chemical Formula 1, or a mixture of a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2; a polymer and a phenyl group in the side chain;

In the above Chemical Formula 1 or Chemical Formula 2, R is one selected from the group consisting of H, a halogen atom, an alkoxy group having 1 to 6 carbon atoms substituted or unsubstituted by a halogen atom, and a combination thereof, and each R may be the same as each other. Or different. Further, R ₁ above is a single bond in which a carbon selected from a benzene ring is directly bonded to an anthracene, an alkylene group having 1 to 8 carbon atoms, and an alkenyl group having 3 to 12 carbon atoms (alken) A ylene group), one of a halogenated alkenyl group having 3 to 12 carbon atoms, an alkynylene group having 3 to 8 carbon atoms, and a combination thereof.

In the film of a specific example of the present invention, the polysiloxane may be a mixture of the compound represented by the above Chemical Formula 1 and the compound of the above Chemical Formula 2 in a weight ratio of 1:1 to 1:5. Polymer.

In the film of one embodiment of the present invention, the polyoxyalkylene may have a weight average molecular weight of 1,000 to 10,000.

In the film of one embodiment of the present invention, the surface-modified ceria may have an average particle diameter of 0.1 to 50 μm.

In the film of one embodiment of the present invention, 0.1 to 10 parts by weight of the above polyoxyalkylene oxide may be contained with respect to 100 parts by weight of the cerium oxide particles.

In the film of one embodiment of the present invention, the haze value of the film can be from 0.5 to 2.0 based on ASTM D1003. Further, the surface hardness may be 2H to 3H which satisfies the pencil hardness measurement (loading speed of 1 kg load speed of 180 mm/min).

According to the surface-modified ceria particle of the present invention, since the particle surface of the ceria is bonded with a phenyl group-containing polyoxane, the molecular behavior thereof is such as that of a polyfluorene or the like containing a plurality of aromatic rings. The molecular behavior of the polymer is very similar. Therefore, while improving the compatibility and dispersibility of the polymer, the physical properties of the inorganic substance can be maximized, thereby obtaining a surface strength. A polymer composite having excellent properties, in particular, a polyimide film can be obtained.

According to an embodiment of the present invention, there is provided a surface-modified cerium oxide, wherein the surface-modified cerium oxide is a cerium oxide particle modified by a polyoxyalkylene oxide, and the polyoxy siloxane is a polymer of a single compound represented by the following Chemical Formula 1, or a mixture of a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2, and a phenyl group in a side chain;

In the above Chemical Formula 1 or Chemical Formula 2, R is one selected from the group consisting of H, a halogen atom, an alkoxy group having 1 to 6 carbon atoms substituted or unsubstituted by a halogen atom, and a combination thereof, and each R may be the same as each other. Or different. Further, R ₁ above is a single bond in which a carbon selected from a benzene ring is directly bonded to an anthracene, an alkylene group having 1 to 8 carbon atoms, and an alkenyl group having 3 to 12 carbon atoms (alken) A ylene group), one of a halogenated alkenyl group having 3 to 12 carbon atoms, an alkynylene group having 3 to 8 carbon atoms, and a combination thereof.

a polymer of a single compound represented by the above Chemical Formula 1, or a mixture of a compound represented by the above Chemical Formula 1 and a compound represented by the following Chemical Formula 2, and a polyphenylene oxide having a phenyl group in a side chain. The alkane is reacted with the -OH group present on the surface of the ceria by reaction with cerium oxide, whereby a bond can be formed. In particular, when a polysiloxane containing a phenyl group is bonded to the surface of the cerium oxide particle, compatibility and dispersibility with a polymer containing a plurality of aromatic rings can be improved.

The compound represented by the above Chemical Formula 1 is not limited, but may, for example, be diphenylsilandiol (DPSD), diphenyldiethoxysilandiol (diphenyldiethoxysilandiol) or diphenyldibutoxide. Diphenyldibuthoxysilandiol and the like.

Further, although the compound represented by the above Chemical Formula 2 is not limited, it is more preferably selected from the group consisting of phenyl trimethoxysilane (PTMS, Phenyl trimethoxysilane), phenyl triethoxysilane (PTES, Phenyl triethoxysilane), and combinations thereof. Any of them.

In a preferred embodiment, the polyoxyalkylene oxide used for modifying the surface of the ceria particle is 1:1 to 1: if the compound represented by the above Chemical Formula 1 is compounded with the compound of the above Chemical Formula 2: When the weight ratio of 5 is a mixture of the polymers of the mixture, it is more advantageous for the degree of packing/packing between the input ceria mixtures, and more excellent can be obtained. Surface hardness.

It is predicted that the compound represented by Chemical Formula 1 can be reduced in yellowness by increasing the pitch of the main chain, and the compound represented by Chemical Formula 2 can increase the filling between the cerium oxide and thereby act to increase the surface hardness.

Further, the weight average molecular weight of the polyoxyalkylene is preferably from 1,000 to 10,000. In the present invention, an apparatus capable of measuring the molecular weight of a polymer such as MALDS (Matrix-Assisted Laser Desorption Ionization Mass Spectrometer) or GPC can be used to measure the weight. Average molecular weight. When the weight average molecular weight of the polyoxyalkylene is in the above range, the polymerization can be sufficiently formed, and the effect of improving the hardness can be exhibited, and it is preferable from the viewpoint of preventing turbidity caused by the coagulation phenomenon with the polymer afterwards. .

According to a preferred embodiment of the present invention, the surface-modified ceria may have an average particle diameter of 0.1 to 50 μm even in the case where the surface is modified with a polyoxyalkylene group, due to the polyoxyalkylene oxide. Very small, therefore, the size of the cerium oxide particles is almost the same as the size before the modification. When the average particle diameter of the surface-modified cerium oxide is within the above range, it is advantageous in terms of the expression effect in the case of being used in a film, and is also advantageous in terms of control when particles are used.

When it contains 0.1 to 30 parts by weight of the above polyoxyalkylene oxide per 100 parts by weight of the cerium oxide particles, it can be advantageously used for surface modification, and more preferably, it can contain 1 to 20 parts by weight, optimally It may contain 5 to 10 parts by weight.

There is no limitation on the method of preparing the surface-modified ceria as described above, and for example, a method of preparing a surface-modified ceria comprising the following steps can be provided. (a) reacting a single compound represented by Chemical Formula 1 or reacting a compound represented by Chemical Formula 1 with a compound represented by Chemical Formula 2 at a ratio of 1:1 to 1:5 to prepare a polyoxyalkylene oxide And (b) adding the polyoxyalkylene obtained in the above step (a) to a solvent in which the cerium oxide particles are dispersed, thereby performing the reaction.

In a preferred embodiment of the present invention, the reaction of the above step (a) is a hydrolysis reaction and a condensation reaction in a chain reaction to prepare a polyoxyalkylene chain, and is carried out by stirring at a temperature of 70 to 90 ° C. 5 to 12 hours. If the temperature is too low or too high, the reaction solvent and The raw materials are easily volatilized and cannot sufficiently cause a reaction within the above time.

At this time, an alcohol and water which are by-products of hydrolysis and polycondensation at the time of the above reaction are generated, and by removing these by-products, the reverse reaction can be reduced, and the progress of the positive reaction can be induced, whereby the reaction rate can be adjusted. Further, at the end of the reaction, the alcohol and water remaining in the polyoxane can be removed by applying a condition of 80 to 100 ° C for 10 minutes or more under reduced pressure, but it is not limited thereto.

In a preferred embodiment of the present invention, the polyoxyalkylene obtained in the above step (a) may have a weight average molecular weight of 1,000 to 10,000 for the above reasons.

Further, in a preferred embodiment of the present invention, the cerium oxide particles in the above step (b) preferably have an average particle diameter of from 0.1 to 50 μm. The cerium oxide is formed by hydrolysis and condensation reaction of alkoxy oxane in the presence of water and a catalyst, and any cerium oxide obtained by a usual synthesis method can be used. However, if the cerium oxide particles are less than 0.1 μm, there is a problem in the application of polyoxyalkylene because the particles are too small, and if it exceeds 50 μm, the particles are too large to be controlled, and therefore, the size is preferably used. Particles within the above range.

In a preferred embodiment of the present invention, the solvent for dispersing the cerium oxide particles is preferably one or more lower alcohols selected from the group consisting of water, methanol, ethanol, propanol, isopropanol and butanol; Any of a mixture of solvents. More preferably, water or a mixed solvent of water and a lower alcohol can be used.

In a preferred embodiment of the present invention, in the above step (b), based on 100 parts by weight of cerium oxide, in the case of adding 0.1 to 30 parts by weight of polyoxyalkylene, an effective surface modification can be performed. It is advantageous in terms of quality, and more preferably, it may be added in an amount of from 1 to 20 parts by weight, and most preferably, it may be added in an amount of from 5 to 10 parts by weight.

In a preferred embodiment of the present invention, the reaction of the above step (b) is: when dispersed in a solvent, polycondensation occurs between the OH group and the polyoxyalkylene on the surface of the hydrolyzed ceria particles. The reaction to form a mesh form is preferably carried out at room temperature for 5 to 10 minutes in consideration of the yield of the reaction. Further, the stirring speed can be appropriately adjusted depending on the content of cerium oxide and water to be used.

In particular, in order to further promote the above step (b), in a preferred embodiment of the present invention, it may be selected from the group consisting of cerium oxide, ammonia (NH ₄ OH), potassium hydroxide (KOH), and sodium hydroxide (NaOH). The above step (b) is carried out under any of the basic catalyst conditions of the mixture, but is not particularly limited in the present invention. More preferably, cesium hydroxide or ammonia can be used as the basic catalyst.

Further, in another embodiment of the present invention, a polyimide film comprising the surface-modified ceria having the above surface may be provided. At this time, the preparation method of the polyimine which can be used is not limited to the method of the present invention, and any method which is generally used can be used. Preferably, the cerium oxide is dispersed in a solution in which the solid component of the polyimine resin obtained in the preparation process of the polyimide is mixed with a solvent. The dispersion can be carried out by physical means such as a mill, a mixer, a high-speed mixer, a homogenizer, and an ultrasonic disperser.

In a preferred embodiment of the present invention, in the preparation of the polyimide film, the surface-modified ceria may be contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of the solid component of the polyimide resin. . If the content of the modified cerium oxide is less than 1 part by weight, the hardness improving effect is very weak, and although the content is increased as the content is increased, if it exceeds 10 parts by weight, the film may become cloudy. This will reduce the optical properties of the film.

Finally, the polyimide film comprising the above-mentioned surface-modified cerium oxide particles has a haze value of preferably 0.5 to 2.0 based on ASTM D1003, and the surface hardness is preferably determined by pencil hardness (load speed of 1 kg load) 180mm/min) 2H to 3H of the reference. In the present invention, the haze value can be measured using a haze meter. An electric pencil hardness tester can be used, and the surface hardness is measured using a Mitsubishi evaluation pencil (UNI) (see the following examples). The properties of the above polyimine film of the present invention are determined by the surface-modified cerium oxide contained in the polyimide film.

That is, unlike the cerium oxide modified by using other functional groups, in the case of the cerium oxide of the present invention, since a polyfluorene oxide containing a plurality of phenyl groups is present on the surface thereof, Since the aromatic ring polymer resin has good compatibility, it has excellent dispersibility, and even if a large amount of particles are present, the film does not become cloudy, and the transparent state can be maintained, and the polysiloxane is high. The molecules can grasp between the surface and the polymer molecules, thus The effect of improving the hardness is achieved. Finally, in the polyimide film containing the above particles, the haze value and the surface hardness in the above range can be achieved.

In the above and the following description, the polyimine is a polyimine which contains a quinone bond in a repeating unit of the main chain, and it should be understood to include a guanamine bond (-CONH- in a part of the main chain). Polyamine-quinone imine.

Example

Hereinafter, the present invention will be described in more detail by way of examples. These examples are only intended to specifically illustrate the invention, and the invention is not limited to the following examples.

Preparation Example 1 Preparation of Cerium Oxide

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) was added as a decane substance. )), stirring at room temperature for 30 minutes. Next, 25 g of NH ₄ OH was slowly added to the above reactor, followed by stirring at the same temperature for 6 hours. After completion of the reaction, the obtained reactant was filtered, and then washed three times with ethanol (50 ml), and dried under reduced pressure in an oven at 40 ° C for 5 hours to obtain 5 g of an average particle diameter of 0.2 μm. Ceria particles (SiO ₂ ).

Here, the morphology and size of the cerium oxide particles were observed by transmission electron microscopy (TEM, 200 kV, JEM-2000EX, JEOL, Japan). The average particle diameter of the particles was measured by an Electrophoretic Light Scattering type Zeta sizer (ELS-8000, Otsuka Electronics, Japan).

Preparation 2 Preparation of polyproline

In a three-necked flask, 40 g of diphenylsilandiol (DPSD, (C ₆ H ₅ ) ₂ Si(OH) ₂ , Sigma Aldrich) and 40 g of phenyltrimethoxydecane (PTMS, C _{6 )} H ₅ Si(OCH) ₃ , Sigma-Aldrich) was mixed by stirring, and reacted at 80 ° C for 10 hours to obtain 60 g of polyoxyalkylene having a weight average molecular weight of 5,000.

Here, gel permeation chromatography (Gel Permeation Chromatography, GPC, ViscoTek), and based on the PS standard to determine polyoxyl The weight average molecular weight of the alkane (unit: g/mol).

Preparation Example 3 Preparation of Surface Modified Cerium Oxide

After dispersing 5 g of the cerium oxide particles obtained in the above Preparation Example 1 in 300 ml of ethanol, 0.5 g of the polyoxy siloxane obtained in the above Preparation Example 2 and 1 ml of NH ₄ OH were added thereto, and at normal temperature. The reaction was carried out for 12 hours to prepare surface-modified cerium oxide particles having an average particle diameter of 0.2 μm. After the reaction was over, the reaction was filtered and washed three times with ethanol (50 ml).

At this time, the particle diameter of the surface-modified ceria particle was measured by the same method as the measurement of the average particle diameter of the above-mentioned ceria particle.

Example 1

In 100 g of N,N-dimethylacetamide (DMAc), 0.1 g (0.1 wt%) of the surface-modified ceria particles prepared in the above Preparation Example 3 was added, using Qsonica (Misonix). The company's 20 kHz ultrasonic disperser was used to disperse to produce a mixed composition.

Embodiment 2 and Embodiment 3

A composition was obtained in the same manner as in the above Example 1 except that the amount of the surface-modified cerium oxide particles was changed to 0.5 g (0.5 wt%) and 1 g (1 wt%), respectively.

Comparative Example 1 to Comparative Example 3

The surface-modified ceria obtained in the above Preparation Example 3, which was added in 100 g of N,N-dimethylacetamide (DMAc), was replaced by 0.1 g (0.1 wt%), 0.5, respectively. G (0.5 wt%) and 1 g (1 wt%) of a surface formed of a -OH component (Nippon Shokubai Co., Ltd., KE-P10, average fineness 0.15 μm) was produced in the same manner as in Example 1. The compositions of Comparative Examples 1 to 3 were obtained.

The haze of the compositions obtained in the above Examples 1 to 3 and Comparative Examples 1 to 3 was measured and described in Table 1 below. At this time, the method of measuring the haze was measured by a haze meter (HM-150 product of Murakaml Color Research Laboratory Co., Ltd.) based on ASTM D1003.

It can be explained that the lower the haze value, the more transparent the film, and the measurement results of the haze are as shown in Table 1 above, and it can be confirmed that the haze values of Examples 1 to 3 are modified by the surface. The excellent dispersibility of the cerium oxide particles to the solvent was significantly lower than that of Comparative Examples 1 to 3.

Example 4

As a *83 reactor, a 1 L reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature regulator and a cooler was used to pass nitrogen through the reactor and filled with 716 g of N,N-dimethyl Acetamine (DMAc), after adjusting the temperature of the reactor to 25 ° C, dissolves 57.64 g (0.18 mol) of TFDB (2,2"-bis(trifluoromethyl)biphenyl-4,4"-diamine (2,2"-bis(trifluoromethyl)biphenyl-4,4"-diamine)), and the solution was maintained at 25 °C. Here, 23.99 g (0.054 mol) of 6FDA (4,4'-(hexafluoroisopropyl isopropyl) diphathalic anhydride) and 7.06 g (0.036) were added. After mol% of CBDA (cyclobutane-1,2,3,4-tetracarboxylic dianhydride), it is stirred for a certain period of time and dissolved and reacted. Thereafter, after maintaining the temperature of the solution at 15 ° C, 18.27 g (0.09 mol) of terephthaloyl chloride (TPC) was added and reacted at 25 ° C for 12 hours to obtain a solid content concentration of 13% by weight. Polyurethane solution with a viscosity of 860 poise.

Next, 34.17 g of pyridine and 44.12 g of anhydrous acetic acid were added to the obtained polyamic acid solution, and the mixture was stirred for 30 minutes, and then further stirred at 70 ° C for 1 hour, and then allowed to stand at room temperature, and then precipitated with 20 L of methanol. The precipitated solid component was filtered and pulverized, and then dried under vacuum at 100 ° C for 6 hours to obtain 95 g of a copolymerized polyamine-quinone imine of a solid component powder.

The above-mentioned 95 g of the copolymerized polyamidoamine-ylidene as a solid component powder was dissolved in 768 g of N,N-dimethylacetamide (DMAc) to obtain a 11 wt% solution, and then, 0.95 g of the surface-modified ceria obtained in Preparation Example 3 was placed and mixed.

The solution obtained above was applied to a stainless steel plate, cast in a thickness of 100 μm, dried by hot air at 150 ° C for 1 hour, dried at 200 ° C for 1 hour, and dried at 300 ° C for 30 minutes, and then slowly. It was cooled and separated from the upper surface of the plate to obtain a 10 μm polyamine-imine film. Thereafter, heat treatment was further performed at 300 ° C for 10 minutes in the final heat treatment step.

Example 5

A 10 μm polyamine-imine film was obtained in the same manner as in the above Example 4 except that the amount of the surface-modified ceria particles was adjusted to 4.75 g.

Comparative example 4

The preparation was carried out in the same manner as in the above Example 4, and a 10 μm-thick polyimide-imine film was obtained without adding the surface-modified cerium oxide at all.

Comparative Example 5

The same procedure as in Example 4 was carried out except that 0.95 g of the filler (Japanese Catalyst, KE-P10, average fineness 0.15 μm) used in the above comparative example was added instead of the surface-modified cerium oxide particles. The method was to prepare a 10 μm polyamine-quinone imine film.

Comparative Example 6

The same procedure as in Example 4 was carried out except that 0.95 g of the filler (Japanese Catalyst, KE-P10, average fineness 0.15 μm) used in the above comparative example was added instead of the surface-modified cerium oxide particles. The method was to prepare a 10 μm polyamine-quinone imine film.

The surface hardness of the film obtained in the above Examples 4 to 5 and Comparative Examples 4 to 6 was measured and described in Table 2. The method for measuring the surface hardness of the above-mentioned film was to use an electric pencil hardness tester, and a Mitsubishi evaluation pencil (UNI) was used, and 50 mm was drawn 5 times at a speed of 180 mm/min at a load of 1 kg, and the surface was measured without scratches. Minimum pencil hardness.

Further, the haze of the films obtained in the above Examples 4 to 5 was measured and described in the surface 2. At this time, the method of measuring the above haze is to use a haze meter (Murakaml). Color Research Laboratory's HM-150 product) was measured based on ASTM D1003.

As a result of measuring the surface hardness, as shown in the above Table 2, it was confirmed that Comparative Example 5 and Comparative Example 6 in which the filler was added showed only the hardness level equivalent to that of Comparative Example 4 (base film), and Example 4 and The polyimine of Example 5 exhibited greatly improved film hardness due to the influence of the surface modified cerium oxide particles of the present invention.

Further, from the results of the haze measurement, it was confirmed that the haze did not increase much even when the cerium oxide particles were added.

Claims (13)

A surface-modified cerium oxide, which is a cerium oxide particle whose surface is combined with a polyoxyalkylene oxide by a OH group, which is composed of diphenyl decanediol and diphenyldiethoxy group. a polymer of at least one compound selected from the group consisting of decanediol and diphenyldibutoxydecanediol, or from diphenyl decanediol, diphenyldiethoxydecanediol, and Polymerization of a mixture of at least one compound selected from the group consisting of phenyldibutoxydecanediol and at least one compound selected from the group consisting of phenyltrimethoxydecane and phenyltriethoxysilane And contain a phenyl group in the side chain. The surface-modified cerium oxide according to claim 1, wherein the polyoxy siloxane is composed of diphenyl decanediol, diphenyldiethoxy decanediol, and diphenyl phthalate. At least one compound selected from the group consisting of butoxystanediol and at least one compound selected from the group consisting of phenyltrimethoxydecane and phenyltriethoxydecane at a ratio of 1:1 to 1:5 The weight ratio of the polymer to the mixture of the mixture. The surface-modified cerium oxide according to claim 1, wherein the polyoxyalkylene has a weight average molecular weight of 1,000 to 10,000. The surface-modified cerium oxide according to claim 1, wherein the surface-modified cerium oxide has an average particle diameter of 0.1 to 50 μm. The surface-modified cerium oxide according to claim 1, wherein the polyoxy siloxane is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the cerium oxide particles. A polyimine film comprising a polyimide resin and cerium oxide particles, the cerium oxide particles being cerium oxide particles whose surface is combined with a polyoxyalkylene oxide via an OH group, and the polyoxy siloxane a polymer of at least one compound selected from the group consisting of diphenyl decanediol, diphenyl diethoxy decane diol, and diphenyl dibutoxy decane diol, or At least one compound selected from the group consisting of decanediol, diphenyldiethoxydecanediol, and diphenyldibutoxydecanediol and phenyltrimethoxydecane and phenyltriethoxy A polymer of a mixture of at least one compound selected from the group consisting of decane and having a phenyl group in the side chain. The polyimine film according to claim 6, wherein the polyoxyalkylene is a diphenyl decanediol, a diphenyldiethoxydecanediol, and a diphenyldibutoxy group. At least one compound selected from the group consisting of decanediol and at least one compound selected from the group consisting of phenyltrimethoxydecane and phenyltriethoxydecane in a weight ratio of 1:1 to 1:5 The polymer of the mixture to be mixed. The polyimine film according to claim 6, wherein the polyoxyalkylene has a weight average molecular weight of 1,000 to 10,000. The polyimine film according to claim 6, wherein the surface-modified ceria has an average particle diameter of 0.1 to 50 μm. The polyimine film according to claim 6, wherein the polyfluorene oxide is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the cerium oxide particles. The polyimide film according to claim 6, wherein the surface-modified cerium oxide particles are contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of the polyimine resin. The polyimine film according to claim 6, wherein the polyimide film has a Haze value of 0.5 to 2.0 based on ASTM D1003. The polyimide film according to claim 6, wherein the surface hardness of the polyimide film is 2H to 3H based on a pencil hardness measurement standard.