TW491873B - Polyimide resin composition and molded articles thereof - Google Patents

Abstract

A polyimide resin composition is disclosed herein which comprises 5 to 60% by weight of a polyimide [polyimide (l)] having a repeating unit represented by the chemical formula 1 and 40 to 95% by weight of a polyimide [polyimide (2)] having a repeating unit represented by the chemical formula 2. According to the present invention, there are provided a polymer alloy in which the advantages of the polyimide (1) and the polyimide (2) are utilized and the disadvantages of the polyimide (1) and the polyimide (2) are reduced; a polyimide resin composition from which crystalline molded articles can be obtained even by a usual molding cycle, for example, an injection molding cycle of about 30 to 60 seconds; and a polyimide resin composition from which molded articles having an excellent dimensional accuracy and flexural modulus can be obtained even by a usual molding cycle, for example, an injection molding cycle of about 30 to 60 seconds, for example, in the case that the molded articles are intended to be used at a high temperature of 230 DEG C or more, for example, a temperature of 230 to 300 DEG C, or 230 to 250 DEG C.

Description

491873 V. Description of the invention (1) ^-! Bright background _ 1 invention collar | m! About a resin group suitable for the manufacture of molded articles can exhibit heat resistance and excellent dimensional stability at high temperatures. ": Koji module 'and by molding the resin composition: molded article at temperature. The J_jj learned from the cutting, polyimide resin is usually used in heat resistance, mechanical properties and chemistry for general general purpose. Engineering plastics are much better, = in terms of performance than engineering plastics. Even if they are "super polymerized, imine resins can be divided into thermoplastics and can be easily molded, so especially in recent years; U and said: the former use The important point of super engineering plastics is that they can be, and increase. Molded and has a high specific gravity. Ge σ can't easily achieve higher characteristics than the traditional stage. Second: From this viewpoint, the dimensional accuracy and yield equivalent of thermal production are already jealous, and the improvement of this performance has been expected. b. Consider polyimide (丨) having a repeating unit represented by Chemical Formula 1. ^ Polyimide (1) having a repeating unit represented by Chemical Formula 1 and +

Disclosed in Japanese Patent No. 4,847, 3 1 1 (Japanese Patent Gazette Please Early Publication I Report 23 6858/1 98 7), and US Patent No. 4,847,349 (Japanese Patent Application Early Public Publication No. 6 88 1 7 / 1 9 87). The polyimide (1) is crystalline, so the glass point (approximately 245 t) and the melting point (approximately 3 88 t) of the polyimide are high, and the heat resistance of the polyimide The rooms are top. Although crystalline, this polyimide has a low

Page 7 491873

It takes a long period of time to perform the polyimide test, for example, the crystallization speed of the injection molding process of about 30 to 60 seconds, in other words, crystals are required. Through the general molding procedure, the obtained molded article is an amorphous phase. Therefore, as long as the molded article is used at a temperature lower than the glass transition point, its characteristics of dimensional accuracy and bending module coefficient are still excellent. On the other hand, when such a molded article is used at an angle higher than the glass transition point, its bending module coefficient is significantly worse, resulting in a molded article: the shape cannot be maintained, so it is difficult to continue use. If it is attempted to continue to use these molded articles including water submicron (1) at a temperature higher than the glass transition point, the amorphous phase molded article should be heat treated to crystallize it. However, this crystallization sometimes causes problems such as a significant dimensional change in a molded article. Consider polyimide (2) with a repeating unit represented by Chemical Formula 2: Polyimide (2) with a repeating unit represented by Chemical Formula 2 is disclosed, for example, in Macromolecules, Vol. 29, ρ. 135 To 142 " (1996) 〇 · This polyimide (2) is crystalline, and there is a large difference between its breaking point (about 丨 9 〇) and its melting point (about 395 C) value. In addition, it has a high crystallization rate, in other words, the time required for crystallization of polyfluorene is very short. In this regard, in the case of polyimide (丨), the difference between the glass transition point and the melting point is about 1 4 3 ° C. The polydonkey imine (2) is in a crystalline state, and in addition, it has a high crystallization rate as described above. Therefore, in a molded article obtained by a general molding process, such as an injection molding process of about 30 to 60 seconds, basically 491873 in the molding step. V. Description of the invention (3) Even when heat treatment is performed ' The size of the finished crystals on these molded articles varies little. Generally speaking, resins with high crystallization speed have high properties, so that the difference between the dazzle point and the glass transition point is ten: m Ϊ so the transformation point is about 19Gt, which is about 155 lower than that of polyimide ⑴ A problem occurred, that is, the bending modulus coefficient of a molded article of 12, f amine (2) in the range of 150 to 2000 ° C includes a basic phase and a high glass. Summary of the invention of the molded product of polyimide (1) at the transformation point-Biography; the question of technology "One of the objects of the present invention is to provide ° σ Meng, /, can be used polyimide (1) and polyfluorene The point of imine (2), while reducing the shortcomings of polyimide (1) and polyimide (2). Another object of Ming is to provide a polyimide resin composition, and to produce a crystalline molded article, even through an ordinary molding process such as an injection molding process of about 30 to 60 seconds. = Another object of the invention is to provide a polyimide resin composition, which has a molded article with excellent dimensional accuracy from Batu, even through a single shot of a nuclear process, such as about 30 to 6 G seconds injection molding Cheng Yi, for example, in the case of using such molded articles at a high temperature of 23 ° C or above, such as 230 to 300t or 230 to 250 t. This The invention is further-the object is to provide a polyimide resin composition, which can obtain a molded article having an excellent helper module coefficient, even through a usual molding process, such as about 30 to 60 seconds Injection molding process, for example

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1 491873 V. Description of the invention (4) --- and a ′. At a temperature of 230 C or higher, such as 230-300. Examples of using these molded articles at temperatures of 0 ° or 23 ° to 250 ° C. = The inventor of the case has conducted intensive research to try to solve the aforementioned problems, and the result = now, #is obtained by mixing two kinds of each other that are miscible with each other during the brightening period. . Therefore, the present invention has been completed based on this knowledge. In other words, the present invention is characterized by the following aspects. 1. The present invention relates to a polyimide resin neoprene, the spoon of which contains 5 to m by weight of a polymerization unit with repeating units represented by the chemical formula m: amine [polyimide] and 40 to 95% by weight Polyimide with units covered by Chemical Formula 2 [Polyimide (2)]: Chemical Formula 1

Chemical formula 2

Page 10 491873 V. Description of the invention (5) 2. In the polyimide resin composition of the present invention described above, the half period of the crystallization time is preferably 0.5 minutes or less. 3. The polyimide resin composition of the present invention described above contains 1 to 100 based on 100 parts by weight of the polyimide resin composition described in paragraph 1 or 2 above. Parts by weight of filler. 4. The polyfe resin composition of the present invention described above contains 5 to 70 parts by weight based on 100 parts by weight of the polyimide resin composition described in the above paragraph 1 or 2. The filler. 5. In the above paragraph 3 or 4, the filler is preferably selected from the group consisting of carbon fiber, carbon black, mica, talc and glass fiber. 6. In the above paragraph 3 or 4, the filler is preferably carbon fiber and / or carbon black. 7. The present invention also relates to a molded article including the polyimide resin composition described in paragraphs 1 to 6 of the above paragraphs. 8 · The above-mentioned molded article is characterized in that differential scanning calorimetry (DSC) is performed at a temperature rising rate of 10 ° C / min within a measurement temperature range of 20 to 4 2 0 ° C ^ (differential scanning calorimetry (DSC) ), No exothermic peak of crystallization was observed up to 300 ° C. 9 · Examples of the above-mentioned molded articles include c disks, electrical and electronic parts, electronic parts, automotive parts, and industrial machinery parts. a Simple and early illustration

Fig. 1 shows the relationship between the inconsistency example and the ratio of the Auruni composition obtained in the comparative example, the bending module coefficient at 150 ° C, and 50 °. 〇 j-inch change before and after heat treatment, and half cycle of crystallization time. K

Page 11 491873 V. Description of the invention (6) Detailed description of the preferred embodiment Polyimide (1) The method for preparing polyimide (i) having a repeating unit represented by Chemical Formula 1 is not particularly limited . For example, the polyfluoreneimine (1) can be obtained by reacting 4,4'-bis (3-aminophenoxy) diphenyl with pyromellitic anhydride in the presence or absence of an organic solvent. The obtained polyamidic acid is chemically or thermally imidized to obtain it. The viscosity of this polyimide (1) is expressed in logarithmic viscosity, preferably in the range of 0.1 to 3.0 dl / g, more preferably 0.3 to 20 di / g, and most preferably 0.5 to 1 · 5 dl / g. If the logarithmic viscosity is less than 0 · 1 d 1 / g, the mechanical properties are sometimes insufficient. If it exceeds 3 · 0 dl / g, the flowability is poor and sometimes injection molding cannot be used. In addition, the logarithmic viscosity referred to here means that the polyfluorene imide powder at 0.05 g is added and dissolved in a mixed solvent of 100 m 1 parachloropan / pan (weight ratio = 9/1), and then 3 Measured at 5 ° C. In a preferred embodiment, the polyfluorene (I) has about 2 4 5. 〇The glass transition point and a melting point of about 38.8 ° C. This polyimide (1) is commercially available under the trade name Aurum (manufactured by itsui Chemical Company). Polyimide (2) = There is no particular limitation on the method for preparing polyimide (2) having a repeating unit represented by Chemical Formula 2. For example, the polyfluoreneimine (1) can be reacted in the presence of a 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride 5 organic solvent by the presence of a right amine-phenoxy) benzene, The resulting polyamic acid was then subjected to

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Prepared by chemical or thermal acid imidization. The viscosity of this polyimide (2) is expressed as a logarithmic viscosity, preferably in the range of 0 ° to = · 〇 = 4, more preferably 0.3 to 2.0 dl / g, and most preferably 0 to 5 1. bd 1 / g 〇 If the logarithmic viscosity is less than u dl / g, sometimes the mechanical properties are not equal to 3.0 dl / g, the flow ability is poor and sometimes it cannot be used. The logarithmic viscosity referred to here is defined as above. π ® ^ In a preferred embodiment, the polyimide has a glass transition point of about 190 ° C and a melting point of about 395 ° C.

The composition ratio of the polyfluorene imine is: An important special requirement of the present invention is the mixing ratio (based on weight) between the polyfluorene and the fluorene.混合 The mixing ratio of the polyimide (1) / polyimide (2) is preferably in the range of 60/40 to 5/95, and more preferably 50/50 to 10, based on the weight. / 9〇, the maximum value is 40/60 to 20/80. If the ratio of polyimide (2) is less than 40%, the molded article obtained from the composition sometimes cannot be used at 23 or below, and if it exceeds 95%, it is at 50%. The bending mode coefficient in the range from 2000 to 2000 sometimes cannot be improved.

Regarding the characteristics of the polyimide resin composition of the present invention: The characteristics of the polyimide resin composition of the present invention will be described below. For example, the molded article obtained from this composition is desired to be 150 to 250. In the case of N = used for μ, it is necessary to pay attention to the bending module coefficient from the viewpoint of maintaining the shape of the molded article. In other words, the bending module coefficient is maintained at a certain average level at a temperature of f to high temperature, and i is balanced

Page 13 491873 V. Description of the invention (8) The bending module coefficient and dimensional accuracy are very important. Regarding polyimide (1), the required crystallization time is very long, that is, the crystallization speed is very slow ', and in the case of general injection molding, a separate amorphous phase molded article is basically obtained. The usable temperature of the amorphous phase molded articles of polyimide (1), that is, the general heat-resistant temperature, depends on the glass transition point, and it is limited to about 230 ° C. Even though molded articles with this heat-resistant temperature have been considered to be quite excellent, the requirements on the market are increasing. Therefore, it is now required that molded articles can be used at temperatures of 230 ° C or lower, such as Mo to 300. 〇 or 230 to 250 ° C :. If the crystallization is completed by heat treatment, the available temperature depends on the melting point, but the shrinkage will increase with the crystallization, so that the dimensional accuracy can be obtained again. Satisfaction It can be understood from the foregoing that one advantage is accompanied by one two points. In terms of w, the crystallization time required for the polyimide (2) 'is short, and J = a crystalline phase molded article is obtained from the initial stage. Even when these clothing items are heat-treated, the size change is still determined by the movement of the knife chain. In some types of polymers, the temperature difference between the melting point and the melting point of the glass Λ, the higher the melting point of the crystallization rate! It is 7 times above. Compared with polyimide 0), polyimide (2) amine (^ same as c, but the glass transition point is lower or even 55). Molding near Polyurethane is sufficient for crystallization, but at the glass transition point, the imine (1) has a difference of 15 ° to 2 °° C. The coefficient of the curvature module is stricter than that of the polymer with the composition ratio. definition:

491873

Under the strict composition ratio of the products, the decisive performance of the products of the present invention will be considered by the inventors, and the definition of the polyimide tree according to the present invention will be explained. In the case of changing the priest, the mouth is dead—and ^ 佚 & only the special function effect can be shown here. There is not always a clear definition of the polyfluorene imine resin mechanism of the present invention, but this problem can be solved simply by mixing the crystalline phase polyamine. However, this assumption is wrong, but the acid imine and the amorphous phase which are not solved by the present invention are wrong. _ ^ 5 a, a $ = The effect of the fine crystals of lipids floating on the matrix of the amorphous phase resin, the effect of Mao Ming cannot be obtained, and it is usually harmful to the crystallization of the crystalline phase resin. In the embodiment of the present invention, the composition is molded through a heating / melting step as a premise. However, the results obtained from differential scanning calorimetry (hereinafter abbreviated as DSC) from the differential scanning calorimetry strongly suggest that the conditions of the embodiment of the present invention and the fine crystals of the crystalline phase resin simply float on the matrix of the amorphous phase resin. The situation is different. In other words, when the molded article of the polyimide C1) is heated from normal temperature, the exothermic peak of the π ′ junction aa appears at 300 °. 〇 Nearby. When the temperature is further increased, the endothermic peak of the 'melt appears, but the heat at this time is about the same as the exotherm of the crystal. In other words, it is understood that in the initial stage, the molded articles were not crystallized at all. On the other hand, in the molded article of polyimide (2), no results were observed.

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Said: the exothermic peak, the towel only appeared melting endothermic. In addition, this absorption is equal to the one described in the example of polyimide (丨). In simple words, the warrior said ..., it was completed in the beginning. In the molded articles according to the resin composition of the present invention, the crystals did not appear on the soil. 'Only the dazzling endothermic heat was observed, and its heat was substantially equal to g squammine (1) or 1 fe (2) is an example of a separate substance. In other words, in both the polyimide (1) and the polyimide (2) in the composition, 'two crystals are OK, and therefore the polyimide (2) should be rejected alone. Therefore, “the π crystal plus the crystal π property can be obtained,” and this obligate Wu is considered to cause the bending mode to these molded articles. The bending module coefficient and the shrinkage are not the π amorphous and the crystal. The maintenance of the coefficient and the balance between the degree. Both polyimides were completely dissolved in each other in a melting / kneading step, and they were transparent, but in a cooling step, they immediately crystallized and became cloudy. In other words, it can be assumed that the polyimide (1) molecule is repelled due to the phase separation of a spino line (spi no dal) and the crystallization of the polyimide (2) in the cooling step, resulting in polymerization. The molecular chain order of the imine (1) has a certain rule, which helps the generation of crystal nuclei or accelerates the molecular chain feed to the surface of the crystal growth, thereby accelerating the crystallization speed of the polyfluorene (1). As can be understood from the foregoing, the above-mentioned problems can be solved by incorporating specific polyimines whose crystallization speeds are different from each other and separated in a cooling step. This composition has not been anticipated so far. However, if the blending ratio of polyimide (1) exceeds 60% by weight, no crystallization can occur. In other words, if the polyimide (2) is excessively diluted with the polyimide (1), the effect of the present invention is lost. In this case, the parties

491873 V. Description of the invention (11) " ~ --------】 = states are dissolved with each other and cured at the same time ', and the importance of this mixing ratio of these molded articles is also from η ς r% 々Ία: Wen 1 Force ”The half period of the crystallization time obtained by reading the constant temperature crystallization measured in μL was added. The half cycle of the crystallization time referred to here has the following meaning, which is a typical factor in measuring the crystallization speed. Eight The composition is heated until it is sufficiently melted, and then quenched to a predetermined temperature, i.e., a glass transition point or higher and a melting point or lower. Time at this point ^ t〇 represents. This composition was fixed and maintained at the temperature at which the crystallization started, and an exothermic peak of crystallization was observed on DSC. The time to obtain this exothermic peak is represented by. Therefore, the half period th of the crystallization time can be represented by the following equation. The measurement technique of th two t!-t〇 half cycle of crystallization time is exemplified in

Macromolecules, Vol. 29, p. 135 to 142 (1996), The

Edited by Society of Polymer Science (Japanese version) in 1973, Polymer Measurement Method, the first volume n, and nNetsu Sokutei ', (calorimetry), V ο 1 · 2 2, p · 1 6 (1 9 9 5). The smaller the half-cycle value of the crystallization time, the higher the crystallization speed. Generally speaking, the half period of this crystallization time depends on the temperature required for crystallization, and it takes a minimum value at the temperature between the glass transition point and the melting point. The minimum half-cycle of the crystallization time of polyimide (1) can be obtained around 320 ° C, which is about 15 minutes. On the other hand, polyimide (2) can be attached at 3 1 0 ° C.

Page 17 491873 V. Description of the invention (12)

At one level, the polyacid sub-time of the time is nearly obtained, and even about the same as the present invention. However, half of the time is generally followed by no special sheet fiber, fossil fiber, which is about 0.2 minutes. At this temperature, the half cycle is too short to be measured successfully. In any case, it is obvious that the half-cycle of the crystallization time of the amine (2) is about two times shorter than that of the polyimide (1), and the crystallization of the polyimide (2) is so fast. λ In the composition containing less than 60% by weight polydonimine (1), one of the examples is still shown to be a half period of the crystallization time with polyimide (2) alone: the number of digits , Which is 0.5 minutes or less. When the mixing ratio of dextroimine (1) exceeds 60% by weight, the crystallization period increases by one digit or more. In other words, crystallization is sometimes easily achieved by injection molding or similar techniques. 9 'will explain one embodiment of the present invention. The filler added to the polyfluorene imide resin composition of the present invention is not limited. Examples of typical fillers include inorganic reinforcements such as fibers, needles, and particles. Examples include carbon fiber, glass fiber, metal fiber, and Ishido. ,anti

Examples of needles include potassium titanate crystal filaments, aluminum borate crystal filaments, carbon knots, filaments, calcium carbonate crystal filaments, natural calcium silicate, zinc oxide crystal filaments, and titanium oxide crystal filaments. Examples of flakes include mica, glass flakes, talc, sericite, kaolinite, nitrite, graphite, and metal flakes. Examples of the particles include magnesium carbonate, calcium carbonate, broken glass beads, silica, duuric acid lock, and metal powder. ° Other examples of inorganic reinforcements include anti-wear modifiers such as quartz powder

Page 18 491873 V. Description of the invention (13) Molybdenum disulfide, fire and hydroxide ballast, anti-track calcium silicate, talc, zeolite, various improvements in various properties. These inorganic reinforcements are used, and the polyimide resin group is preferably used in an amount of 3 to 85 parts by weight: if the effect of the inorganic reinforcement is physical, but if it is supercapacity, it may be harmful. Flame retarding modifiers, such as antimony trioxide, aluminum hydroxide trace modifiers, such as asbestos, acid resistance modifiers, such as metadiatomite, alumina, white sand balls, hydrated alumina, water metal oxides, and carbon black, and It can be used for various options. The amount of the inorganic reinforcement, alone or in the form of a mixture of two or more, is in the range of 1 to 100 parts by weight, more preferably 5 to 70, relative to 100 parts by weight of the product. Parts by weight. The amount is less than 1 part by weight, and sometimes cannot be shown to be stronger than 100 parts by weight, and sometimes it is flowable during molding. As a third fat. Can also be mixed. A polymer that can be mixed with acid S, polyacetal, acetal, polyacrylamide, and a homopolymer of liquid crystal. An appropriate amount of a resin can be added to the polyimide of the present invention as a third component. In order to meet the purpose of use, as long as this is not hindered. There is no particular limitation on the kind of resin that can be added as the third component of the polyfluorinated product of the present invention. The resin can be a suitable heat, polyacrylic acid, acetonitrile, etc A typical example is a thermoplastic tree equivalent of other thermoplastic resins. According to the purpose, plastic resins include polyolefins, polystyrene, polycarbamines, polyamido-imino, polyphenylene ether, poly, polyimide. Phenylsulfide, polyimide, polyketone, polyether, and polyimide having the same properties as those used in the present invention

Page 19 491873 V. Description of the invention (14) It can be used as a fluororesin such as polytetrafluoroethylene and the side "Purpose" In addition, it has the characteristics of model separation and wear / friction. Choosing monoamine fibers is also good for improving mechanical properties. It can be used alone or in the form of a mixture of two or more. It is called the other two: colorants, release agents, various stabilizers, plasticizers, and oils can be added to the polyimide resin composition as long as the object of the present invention is not hindered. (1) In the present invention, the polyimide resin composition can be made by uniformly mixing polyimide ^ ΓΛ 2 2), and other groups f ☆, and then used a single spiral to roll on 1 2 Extrusion is continuously produced to extrude the mixture. Batches can also be made using a batch system using a hybrid = *, a softener, a Brabender device, or the like. The i: ΐ f lipid composition can be produced primarily by injection molding or transfer molding. Molding side & 'If extruded and compressed ;;]] Poly "amine resin composition changes over a wide temperature range, & Wu' can control the size of molded articles within a small range is high The ruler + 22 is used for moldings σ that are used at a high temperature of 23 0 ° C or above and require 0-inch accuracy. The collar of the semiconductor container can be used for τ Γ U In other domains, the disks of the polydonimide resin composition wafers of the present invention, and those used in the 1c process ^ In the field of electricity and electronics, materials can be used for manufacturing, production, and 7-member domains. The imine resin is used to make clothes connectors, sockets, spools, and used to make hard disks.

491873 V. Description of the invention (15) Machine tool fixtures for carrier, LCD screen carrier, etc., and disk for quartz oscillator. In the field of parts for office supplies, the polyimide resin composition of the present invention can be used for manufacturing a folder of a photocopier, a thermally insulated bearing of a photocopier, a gear of a photocopier, and the like. In the field of automotive parts, the polyimide resin composition of the present invention can be used for manufacturing thrust washers, transmission rings, piston rings, oil seal rings, and the like. In the field of industrial machinery parts, the polyimide resin composition of the present invention can be used for manufacturing retardation positioners, pump gears, conveyor chains, sliding sleeves for extension machines, and the like. Next, the present invention will now be described in more detail based on examples, but the scope of the present invention should not be limited to these examples. Incidentally, the measurement and evaluation of the physical properties of resins in the examples and comparative examples are performed by the following steps. (A) Half cycle of crystallization time The method for measuring the half cycle of crystallization time has been described above. In other words, the half period of the crystallization time is measured by a constant temperature crystallization test using a differential scanning calorimetry (DSC). The composition is heated to be sufficiently melted, and then quenched to a predetermined temperature. The time at this point is represented by tQ. This composition was fixed and maintained at the temperature at which the crystallization started, and an exothermic peak of crystallization was observed on DSC. The time to obtain this exothermic peak is represented by h. Therefore, the half period th of the crystallization time can be represented by the following equation. th = L-t〇 The smaller the half-cycle value of the crystallization time, the higher the crystallization speed. Generally speaking,

Page 21 491873 V. Description of the invention (16) The half period of this crystallization time depends on the temperature required for crystallization, and it takes a minimum value at the temperature between the glass transition point and the melting point. Therefore, note here that the half-cycle value of the minimum crystallization time measured at a temperature change from 190 ° C to 320 ° C. In the case where the half period of the crystallization time is shorter than 0.2 minutes, the measurement by the helmet method 'is therefore expressed as < 0.2. … (B) Dimensional changes. The dumbbells of ASTM No. 1 (ASTMD-63.8) were heat-treated at 30 ° C for 2 hours, and the width of the parallel part of the dumbbells was measured with sliding calipers before and after treatment to observe the dimensional changes. (C) Bending module coefficient For a sample that has been heat-treated under the same conditions as in (B) above, the bending module coefficient is measured according to ASTMD-790, cross temperature. The measurement temperature is two degrees, 23 ° C, 150t And 250 ° C. · Example of the preparation of polyimide (2) Put 2 04 · 4 g (0.7 mol) in a six device equipped with a mixing device, a reflux condenser, and a nitrogen introduction tube. Of 1,3-bis (4-aminobenzyloxy) benzene, 199.6 g (0.679 mol) of 3, 3,4,4—dibenzyltetracarboxylic acid " diacid anhydride ' 6.22 g (0.06 mol) of phthalic anhydride, and phenol at between 48 and 80 g, and then heated to 200 ° C under stirring with nitrogen gas phenol. After that, it should be at 200 It was carried out for 4 hours, at this time, after confirming that about 9 m 1 of water had flowed out and the reaction solution was complete, the reaction solution was cooled to room temperature, and then about 20% of toluene was added thereto, and then collected by filtration. The end of the obtained polyimide square, followed by drying the thus obtained polyimide (2) for logarithm &. 2) powder d1 / g. The number of degrees is 0.

Page 22 491873 — 丨 _ V. Description of the invention (π) f Examples 1 to 5 Polyimide (1) (manufactured by M i t s u i Chemical Co., Ltd., trade name

Aurum PD450 'Log viscosity = 0.45 dl / g), polySiimine (2) obtained in the above preparation example, and carbon fiber (manufactured by T 〇h 〇 R ay ο η company) under the trade name ΗΤ A -C6) are each mixed in the proportions shown in Table i, and then thoroughly mixed using a tumble mixer. The mixture was melted, mixed, and extruded at a screw speed of 42 ° C ^ 80 rpm with a twin-screw extruder with a 37 mm screw diameter and L / D = 32 to obtain pellets. The half cycle of the crystallization time of the beads thus obtained was measured. In addition, these pellets were shot at a molding temperature of 4 200 C and a molding temperature of 210 at a molding process of 30 seconds, and the obtained samples were evaluated. The results are shown in the table. Results The mixing ratios between each polyimide (1) and fish extractor (Dongyun) were prepared as shown in Table 2 in Table 1-Master A. Examples 1 to 3 The same procedure was used for evaluation. Comparative Example 3 was evaluated using polyimide (1. Results of Comparative Example 4). The individual substances are shown in Table 2 together with the phases in Examples 1 to 3.

The evaluation was performed using polyimide (1. step). • Results are shown in the early table. The quality is synchronized with the phases in Examples 1 to 3. Li Li G and the Aurum composition obtained in the example * 2 bending mode. Group coefficient, heat treatment at 150 ° C

Page 23 491873 V. Description of the invention after dimensional change (18) and half cycle of crystallization time. * _1 Example 1 2 3 4 5 Polydonimide resin (1) 5 10 30 50 60 Composition (pt S. Polyimide resin (2) 95 90 70 50 40 wt.) Carbon fiber 30 30 30 30 30 half Crystallization time (min) < 0. 2 < 0 · 2 < 0 · 2 0.4 0. 5 Dimensional change (%) Bending module coefficient (MPa) 0. 55 0. 60 0. 62 0. 70 0. 70 2 3 ° C 2 2 0 0 0 2 2 0 0 0 22 0 0 0 2 3 0 0 0 2 3 5 0 0 1 50 ° C 1 6 5 0 0 1 70 0 0 1 8 0 0 0 1 8 0 0 0 1 8 0 0 0 2 5 0 ° C 6 5 0 0 70 0 0 82 0 0 8 3 0 0 8 5 0 0

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491873 V. Description of the invention (19) Comparative example 1 2 3 4 Polyimide resin (1) 1 80 100 0 Composition Polyimide resin (2) 99 20 0 100 (pts.wt.) Carbon fiber 30 30 30 30 Semi-crystallization time (mi η) < 0. 2 14. 0 14. 2 < 0 · 2 Dimensional change (%) 0.12 1. 30 1.33 0. 1 0 Bending module coefficient (MPa) 2 3 t 2 0 0 0 0 21000 21000 2 0 0 0 0 15 (TC 1 0 0 0 0 1 80 0 0 1 8 0 0 1 0 0 0 0 2 5 0 ° C 4 500 75 0 0 8 0 0 0 44 00 The present invention The effect is as follows. The first effect of the present invention is to provide a polymer alloy which can take advantage of polyimide (1) and polyimide (2), and reduce polyimide (work) and polymer. Disadvantages of fluorene imine (2). A second effect of the present invention is to provide a polyfluorene imine resin composition from which a crystalline molded article can be obtained, even through a usual molding procedure, such as about 3 0 to 60 seconds injection molding process. A third effect of the present invention is to provide a polyimide resin composition, which can obtain a molded article having excellent dimensional accuracy, even by using Often flat molding procedures, for example from about 3 billion 6〇 seconds to injection molding procedures, for example the tongue 'to be at or above the temperature at 2 3 0 ° C, such as 230 or 230 ° c to 3〇〇

Page 25 ^ 1873 V. Description of the invention (20) to 250 ° C, the use of these molded articles in the example. The fourth effect of this description is to provide a polyimide resin composition, which can be used to produce a molded article having an excellent% curvature modulus, even through a usual molding process, such as about 30 to 60 seconds. The injection molding process, for example, at high temperatures of 230 ° C or higher, such as 230 to 300 ° C or 230 to 250. (: In the case where these molded articles are used at a temperature of (:).

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Claims (1)

Cl. Case No. 87121600 Λ_η Amendment 9! Τ ^ ΓΤΠΠ 1. A polyimide resin composition comprising 5 to 60% by weight of polyimide having a repeating unit represented by Chemical Formula 1 [Polyimide Peryleneimine (1)], and 40 to 95% by weight of polyimide [polyimide (2)] having repeating units represented by chemical formula 2, the percentage ratio is based on polyimide ( 1) Add the total weight of polyimide (2): Chemical formula 1 〇II 0 ⑴ Chemical formula 2 General ο ★ ο Its substances form lipids. Tree oligoamine is more subordinary or 醯 Zhong Ju gathers the 5th paragraph Fan Li special request Zhongru 2 for the half-time period of time to crystallize the composition: Group Di Zhiwei tree Fan amine Lean special please ask to apply for The amount of 11 items is yi fen fen ο / r 巳 ο I 1 is specifically for the application, please include as described in the package • 5 3 of the narratives in the above description, and the CC property will be wai ί aA- 巳 Au 々々 库 -___ 匕Said people, and trees specifically for amines, please ask Yashen to brew such as poly-4, and the amount of the filling is ο ο to IX to Wucheng into a group of the first fat Wai tree amines The amount of the item is the same as that described in the item \\ 326 \ 2d- \ 91-02 \ 87121600.ptc Page 28 491873 The polyimide resin composition has a filler content of 5 to 70 parts by weight. 5. The polyimide resin composition according to item 3 of the application, wherein the filler is at least one selected from the group consisting of carbon fiber, carbon black, mica, talc and glass fiber. 6. The polyimide resin composition according to item 5 of the application, wherein the filler is carbon fiber and / or carbon black. 7-A molded article made of the polyimide resin composition described in item 3 of the scope of patent application, wherein when the measurement temperature range of 20 to 420 ° C is 1 When differential scanning calorimetry (DSC) was performed at a temperature rising rate of 0 ° C / mi η, no crystal exothermic peak was observed at 260 to 300 ° C. 8 · If the molded article in the scope of patent application No. 7, it can be used for trays. 9 · If the molded article in the scope of patent application item 7, it can be used for electrical or electronic parts. 10. If the molded article in the scope of patent application item 7 is used, it can be used for office parts. 1 1. If the molded article in the scope of patent application No. 7 is used, it can be used for auto parts. 12,12 If the molded article in the scope of patent application item 7 can be used in industrial machinery W326 \ 2d- \ 91-02 \ 87121600.ptc Page 29