Polyimide resin having excellent dimensional stability and high flexural modulus and manufacturing method therefor

Abstract

The present invention relates to a polyimide resin which has excellent dimensional stability in a high-temperature and moisture-exposed environment, and a manufacturing method therefor.

Description

Polyimide resin with excellent dimensional stability and high flexural modulus and method for producing the same

[0001] The present invention relates to a polyimide resin having excellent dimensional stability in high temperature and moisture exposure environments and a method for producing the same.

[0002] Polyimide resin is generally a high-temperature-resistant resin manufactured by reacting an aromatic tetracarboxylic acid or its derivative with an aromatic diamine or aromatic diisocyanate, followed by imidization. Polyimide resin can have various molecular structures depending on the type of monomer used.

[0003] Polyimide resin has no melting point, making it difficult to uniformly disperse it when mixed with additives. In addition, since molded products require compression molding and high-temperature sintering at high temperatures and pressures, unevenly dispersed additives can cause defects in the molded products.

[0004] Specifically, defects caused by uneven distribution can degrade the mechanical and thermal properties of molded parts. This can lead to warpage, cracking, and dimensional changes in molded parts under high-load, high-temperature, and repetitive load environments.

[0005] Modern manufacturing industries such as semiconductors, displays, aerospace, and military demand ever higher standards for materials, components, and equipment to produce sophisticated, integrated products. To meet these demands, the materials industry is striving to develop materials with superior dimensional stability and long lifespan.

[0006] As a result, there is a need to develop a polyimide resin and manufacturing method that have excellent dimensional stability, high flexural modulus, low coefficient of thermal expansion, and low moisture absorption.

[0007] The purpose of the present invention is to provide a polyimide resin having excellent dimensional stability, high flexural modulus, and low coefficient of thermal expansion, and a method for producing the same.

[0008] The purpose of the present invention is not limited to the purposes mentioned above. The purpose of the present invention will become more apparent from the following description, and may be realized by the means and combinations thereof described in the claims.

[0009] A polyimide resin according to one embodiment of the present invention comprises a reaction product of a diamine compound and a dianhydride compound, and may have a thermal dimensional change rate of 0.02% or less as measured below.

[0010] [Thermal dimension change rate]

[0011] When a Φ2.5mm hole is machined at 30mm intervals in a molded product measuring 35mm in width, 35mm in length, and 5mm in height, and the molded product is exposed to an air atmosphere of 150℃ to 200℃ for 3 to 5 days, the rate of change in the position of the hole is measured as follows.

[0012] Position change rate [%] = {(hole spacing after environmental exposure - hole spacing before environmental exposure) / (hole spacing before environmental exposure)} × 100

[0013] A polyimide resin according to one embodiment of the present invention comprises a reaction product of a diamine compound and a dianhydride compound, and may have a humidity dimensional change rate of 0.015% or less as measured below.

[0014] [Humidity dimension change rate]

[0015] When a Φ2.5mm hole is machined at 30mm intervals in a molded product measuring 35mm in width, 35mm in length, and 5mm in height, and the molded product is exposed to an atmosphere of 23℃ to 25℃ and a relative humidity of 50% to 70% for 10 days, the rate of change in the position of the hole is measured as follows.

[0016] Position change rate [%] = {(hole spacing after environmental exposure - hole spacing before environmental exposure) / (hole spacing before environmental exposure)} × 100

[0017] The above polyimide resin may further include at least one additive selected from the group consisting of aluminum silicate (Al2O3·2SiO2·2H2O), titanium oxide (TiO2), aluminum oxide (Al2O3), zirconium oxide (ZrO2), and combinations thereof.

[0018] The content of the above additive may be 30% to 70% by weight.

[0019] The above diamine compound may include at least one selected from the group consisting of p-phenylenediamine (p-PDA), m-phenylenediamine (m-PDA), 4,4'-oxydianiline (ODA), and combinations thereof.

[0020] The above diamine compound may include 85 mol% to 95 mol% of p-phenylenediamine; and 5 mol% to 15 mol% of 4,4'-oxydianiline.

[0021] The above dianhydride compound may include at least one selected from the group consisting of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), 4,4'-oxydiphthalic dianhydride (ODPA), and combinations thereof.

[0022] The above dianhydride compound may include 30 mol% to 70 mol% of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride; and 30 mol% to 70 mol% of pyromellitic acid dianhydride.

[0023]

[0024] *The above dianhydride compound may include 70 mol% to 90 mol% of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride; and 10 mol% to 30 mol% of 4,4'-oxydiphthalic acid dianhydride.

[0025] The molar ratio of the above diamine compound and the dianhydride compound may be 30:70 to 70:30.

[0026] The above polyimide resin may have a flexural modulus of 8,500 MPa or more.

[0027] The above polyimide resin may have a thermal expansion coefficient of 25 ppm / ℃ or less.

[0028] A method for producing a polyimide resin according to one embodiment of the present invention may include the steps of: preparing a starting material including a diamine compound and a dianhydride compound; preparing a mixed solvent including a first solvent that is soluble in the starting material and a second solvent that is insoluble in the starting material; adding the starting material and an additive to the mixed solvent and reacting the starting material to obtain a product; and annealing the product to obtain a polyimide resin.

[0029] The step of annealing the above product to obtain a polyimide resin may be annealing the product at 100°C to 300°C for 5 to 15 hours.

[0030] According to the present invention, a polyimide resin having excellent dimensional stability, high flexural modulus, and low coefficient of thermal expansion and a method for producing the same can be obtained.

[0031] According to the present invention, a polyimide resin having excellent processability and a method for producing the same can be obtained.

[0032] Therefore, the polyimide resin according to the present invention can be used as a key heat-resistant component in various advanced industrial fields such as the electrical and electronic industry, automobile industry, semiconductor industry, and aerospace industry.

[0033] The effects of the present invention are not limited to those mentioned above. It should be understood that the effects of the present invention encompass all effects inferred from the following description.

[0034] The above-described purposes, other purposes, features, and advantages of the present invention will be readily understood through the following preferred embodiments, illustrated in the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments presented herein are provided to ensure that the disclosure is thorough and complete, and to ensure that the spirit of the present invention is fully conveyed to those skilled in the art.

[0035] In describing each drawing, similar reference numerals are used to designate similar components. In the attached drawings, the dimensions of structures are shown exaggerated for clarity of the present invention. Terms such as first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The terms are used only to distinguish one component from another. For example, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component, without departing from the scope of the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise.

[0036] In this specification, it should be understood that terms such as "include" or "have" are intended to specify the presence of a feature, number, step, operation, component, part or combination thereof described in the specification, but do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts or combinations thereof. In addition, when it is said that a part such as a layer, film, region or plate is "on" another part, this includes not only the case where it is "directly above" the other part, but also the case where there is another part in between. Conversely, when it is said that a part such as a layer, film, region or plate is "under" another part, this includes not only the case where it is "directly below" the other part, but also the case where there is another part in between.

[0037] Unless otherwise specified, all numbers, values, and / or expressions expressing quantities of ingredients, reaction conditions, polymer compositions, and blends used herein are approximations that inherently reflect, among other things, the various uncertainties of measurement that arise in obtaining such values, and therefore should be understood as being modified in all instances by the term "about." Furthermore, whenever a numerical range is disclosed herein, such range is continuous and includes every value from the minimum value to the maximum value inclusive, unless otherwise indicated. Furthermore, whenever such a range refers to integers, every integer from the minimum value to the maximum value inclusive, unless otherwise indicated, is included.

[0038]

[0039] The polyimide resin according to the present invention may include a reactant of a diamine compound and a dianhydride compound; and additives. As used herein, "polyimide resin" may refer to a resin composition and / or a molded product manufactured using the composition. Even if the composition and molded product are not distinguished below, those skilled in the art will be able to clearly understand what the polyimide resin refers to based on the context of the sentence.

[0040] The reactant may comprise a copolymer of the diamine compound and the dianhydride compound. The reactant may comprise a unit structure derived from the diamine compound and a unit structure derived from the dianhydride compound. In addition, the reactant may comprise a random copolymer, a block copolymer, or an alternating copolymer.

[0041] The above diamine compound may include at least one selected from the group consisting of p-phenylenediamine (p-PDA), m-phenylenediamine (m-PDA), 4,4'-oxydianiline (ODA), and combinations thereof.

[0042] Preferably, the diamine compound may include 85 mol% to 95 mol% of p-phenylenediamine and 5 mol% to 15 mol% of 4,4'-oxydianiline. The p-phenylenediamine has a rigid structure, and the 4,4'-oxydianiline has a flexible structure. By using these in appropriate amounts, the heat resistance, oxidation stability, and mechanical properties of the polyimide resin can be balancedly improved.

[0043] The above dianhydride compound may include at least one selected from the group consisting of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), 4,4'-oxydiphthalic dianhydride (ODPA), and combinations thereof.

[0044] Preferably, the dianhydride compound may include 30 mol% to 70 mol% of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride and 30 mol% to 70 mol% of pyromellitic acid dianhydride. Alternatively, the dianhydride compound may include 70 mol% to 90 mol% of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride; and 10 mol% to 30 mol% of 4,4'-oxydiphthalic acid dianhydride. The 3,3',4,4'-biphenyltetracarboxylic acid dianhydride has a flexible structure, and the pyromellitic acid dianhydride has a rigid structure. By using them in appropriate amounts, the heat resistance, oxidation stability, and mechanical properties of the polyimide resin can be balancedly improved.

[0045] The molar ratio of the above diamine compound and the above dianhydride compound may be 30:70 to 70:30, or 50:50.

[0046] The above additive may include an inorganic additive. The above inorganic additive may include at least one selected from the group consisting of aluminum silicate (Al2O3·2SiO2·2H2O), titanium oxide (TiO2), aluminum oxide (Al2O3), zirconium oxide (ZrO2), and combinations thereof.

[0047] The content of the above additive may be 30 wt% to 70 wt% based on the total weight of the reactant and additive. If the content of the above additive is less than 30 wt%, the improvement effect on dimensional stability, flexural modulus, etc. may be minimal, and if it exceeds 70 wt%, the content of the reactant may be relatively low, which may deteriorate the inherent properties of the polyimide resin.

[0048] The polyimide resin according to the present invention may have a thermal dimensional change rate of 0.02% or less, as measured as follows. The lower limit of the thermal dimensional change rate is not particularly limited, and may be 0% or more, 0.005% or more, or 0.01% or more.

[0049] [Thermal dimension change rate]

[0050] The above thermal dimensional change rate may refer to the change rate of the position of the hole when holes of Φ2.5 mm are machined at 30 mm intervals in a molded product having a width of 35 mm, a length of 35 mm, and a height of 5 mm, and the molded product is exposed to an air atmosphere of 150°C to 200°C for 3 to 5 days. The change rate of the hole position can be calculated by the following equation.

[0051] Position change rate [%] = {(hole spacing after environmental exposure - hole spacing before environmental exposure) / (hole spacing before environmental exposure)} × 100

[0052] The polyimide resin according to the present invention may have a humidity dimensional change rate of 0.015% or less, as measured below. The lower limit of the humidity dimensional change rate is not particularly limited, and may be 0% or more, or 0.005% or more.

[0053] [Humidity dimension change rate]

[0054] The above humidity dimensional change rate may refer to the change rate of the position of the hole when holes of Φ2.5 mm are machined at 30 mm intervals in a molded product having a width of 35 mm, a length of 35 mm, and a height of 5 mm, and the molded product is exposed to an atmosphere of a temperature of 23°C to 25°C and a relative humidity of 50% to 70% for 10 days. The change rate of the position of the hole may be calculated using the above-mentioned formula.

[0055] The polyimide resin according to the present invention may have a flexural modulus of 8,500 MPa or more, or 8,500 MPa to 15,000 MPa. The flexural modulus may be a measure of how much a target material can bend without being permanently deformed or destroyed. The flexural modulus may be measured according to ASTM D790.

[0056] The polyimide resin according to the present invention may have a coefficient of thermal expansion of 25 ppm / ℃ or less. The lower limit of the coefficient of thermal expansion is not particularly limited, and may be greater than 0 ppm / ℃, greater than 1 ppm / ℃, or greater than 5 ppm / ℃. The coefficient of thermal expansion may refer to the ratio between the thermal expansion and temperature of an object under a certain pressure. The coefficient of thermal expansion may be measured according to ASTM E831.

[0057] The polyimide resin according to the present invention may have a moisture absorption rate of 0.08% or less. The lower limit of the moisture absorption rate is not particularly limited and may be 0.04% or more, or 0.06% or more. The moisture absorption rate may be a measure of the degree to which a sample absorbs moisture. The moisture absorption rate may be measured according to ASTM D570.

[0058] The polyimide resin according to the present invention has excellent thermal dimensional change rate and humidity dimensional change rate, high flexural modulus, and low thermal expansion coefficient and moisture absorption rate, and can be said to be a material that can be widely used in various fields such as semiconductors, displays, aerospace, and military.

[0059] In addition, the polyimide resin according to the present invention has an intrinsic viscosity of 0.7 dl / g to 2.5 dl / g, a crystallinity of 20% to 30%, and a specific surface area of ​​50 m 2 / g to 400m 2 / g, the degree of imidization may be 98% to 99%. Since the polyimide resin has a low degree of crystallinity, a high degree of imidization, and a high specific surface area, it can be effectively compression molded into a molded product.

[0060] A method for producing a polyimide resin according to the present invention may include a step of preparing a starting material including a diamine compound and a dianhydride compound, a step of preparing a mixed solvent including a first solvent that is soluble in the starting material and a second solvent that is insoluble in the starting material, a step of introducing the starting material and an additive into the mixed solvent and reacting the starting material to obtain a product, and a step of annealing the product to obtain a polyimide resin.

[0061] The starting materials, diamine compound and dianhydride compound, and additives are described above, so they are omitted below.

[0062] The present invention is characterized in that the solubility of the mixed solvent in the starting material is finely controlled by combining the first solvent and the second solvent in an appropriate ratio. In addition, unlike the prior art, the azeotropic point and reaction temperature of the mixed solvent can be controlled by combining the second solvent, which has no solubility in the starting material, with the first solvent. Through the solubility and reaction temperature, etc., the apparent density of the final material, the polyimide resin, can be controlled to an appropriate level. The apparent density is a physical property related to the filling amount of the polyimide resin when producing a molded article, and the apparent density of the polyimide resin may be 0.2 g / cm3 to 0.31 g / cm3. When the apparent density of the polyimide resin falls within the above range, fusion between the polyimide resins occurs well, thereby preventing a decrease in the mechanical strength of the molded article.

[0063] The first solvent may include a solvent that is soluble in the starting material. The solubility in the starting material may mean a property of dissolving the starting material by 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%. The unit of the ratio may be mass, volume, or mole.

[0064] The first solvent may include at least one selected from the group consisting of N-methyl-2-pyrrolidone (NMP), dimethylformamide (N,N-dimethylformamide (DMF), dimethylacetamide (DMAc), pyridine, tetrahydrofuran (THF), and combinations thereof.

[0065] The second solvent may include a solvent that is insoluble in the starting material. Insoluble in the starting material may mean dissolving the starting material by 20% or less, 10% or less, or 0%. The unit of the ratio may be mass, volume, or mole.

[0066] The second solvent may include at least one selected from the group consisting of xylene, water, ethanol, methanol, isopropyl alcohol, and combinations thereof.

[0067] The above mixed solvent may contain 58 to 70 wt% of the first solvent and 30 to 42 wt% of the second solvent. When the contents of the first solvent and the second solvent fall within the above range, the effects of the present invention described above can be achieved.

[0068] The product obtained by the above method can be compression molded to obtain a polyimide resin. Specifically, the product is compression molded at a pressure of 50,000 psi to 100,000 psi, the compression molded result is fired in a nitrogen atmosphere at 300°C to 500°C for 5 to 15 hours, and the fired result is annealed in an air atmosphere at 100°C to 300°C for 5 to 15 hours to obtain a polyimide resin.

[0069] The present invention is characterized by providing a polyimide resin having excellent thermal dimensional change rate and humidity dimensional change rate, high flexural modulus, and low thermal expansion coefficient and water absorption rate by adding a specific inorganic additive in a specific amount together with a starting material and annealing the reactant.

[0070]

[0071] Hereinafter, the present invention will be described in more detail through specific examples. The following examples are merely illustrative examples to aid understanding of the present invention and are not intended to limit the scope of the present invention.

[0072]

[0073] Example 1

[0074] A reactor equipped with a Dean-Stark trap, a stirrer, a temperature control device, and a nitrogen injection device was prepared. The reactor was placed under a nitrogen atmosphere.

[0075] A mixed solvent was prepared by mixing 65 wt% of N-methyl-2-pyrrolidone (NMP), the first solvent, and 35 wt% of xylene, the second solvent, and the mixed solvent was introduced into the reactor.

[0076] 85 mol% of p-phenylenediamine (p-PDA), 15 mol% of 4,4'-oxydianiline (ODA), and 50 wt% of aluminum silicate were dispersed in the mixed solvent as diamine compounds. The content of the aluminum silicate is based on the total weight of the starting material and the aluminum silicate. After sufficiently dispersing the diamine compound, 50 mol% of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) and 50 mol% of pyromellitic acid dianhydride (PMDA) as dianhydride compounds were added to the resultant mixture. The molar ratio of the diamine compound and the dianhydride compound was adjusted to 1:1.

[0077] The temperature of the reactor was raised to approximately 70°C and the reaction was conducted for approximately 3 hours. Thereafter, the temperature of the reactor was raised to approximately 150°C and the imidization reaction was conducted for approximately 2 hours. The water generated during the reaction was removed using a Dean-Stark trap.

[0078] When the reaction is complete, the precipitated polyimide polymer is filtered, washed with 2 ℓ of acetone, and then heated at 190℃ for 10 - 1 Dry for 16 hours under vacuum condition of 10 torr and nitrogen flow, 300℃, 10 3 The product was dried for 8 hours under a nitrogen atmosphere of 10 Torr to obtain a powdered product. The product had an intrinsic viscosity of 1.7 dl / g measured at 30°C with a concentration of 0.2 g / dl using concentrated sulfuric acid as a solvent, and an imidization degree of 99%.

[0079] The above product was molded at a pressure of 100,000 psi and sintered at 400°C for 11 hours. Thereafter, to remove residual stress in the sintered product, annealing was performed at 150°C in an air atmosphere for 10 hours to obtain a polyimide resin.

[0080] The composition of the above polyimide resin is shown in Table 1.

[0081]

[0082] Examples 2 and 3

[0083] A polyimide resin was manufactured in the same manner as in Example 1, except that the content of aluminum silicate was changed as shown in Table 1.

[0084]

[0085] Examples 4 to 8

[0086] A polyimide resin was manufactured in the same manner as in Example 1, except that the type and content of the inorganic additive were changed as shown in Table 1.

[0087]

[0088] Comparative Example 1

[0089] A polyimide resin was prepared in the same manner as in Example 1, except that aluminum silicate was not added.

[0090]

[0091] Example 9

[0092] A polyimide resin was prepared in the same manner as in Example 1, except that 90 mol% of p-phenylenediamine (p-PDA) and 10 mol% of 4,4'-oxydianiline (ODA) were used as diamine compounds, and 80 mol% of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) and 20 mol% of 4,4'-oxydiphthalic acid dianhydride (OPDA) were used as dianhydride compounds.

[0093]

[0094] Examples 10 and 11

[0095] A polyimide resin was manufactured in the same manner as in Example 9, except that the content of aluminum silicate was changed as shown in Table 1.

[0096]

[0097] *95

[0098] Examples 12 to 17

[0099] A polyimide resin was manufactured in the same manner as in Example 9, except that the type and content of the inorganic additive were changed as shown in Table 1.

[0100]

[0101] Comparative Example 2

[0102] A polyimide resin was prepared in the same manner as in Example 9, except that aluminum silicate was not added.

[0103] Classification Anhydride [mol%] Diamine [mol%] Additive [wt%] 1) BPDAPMDAODPAp-PDAODAAluminum silicateTiO2Al2O3ZrO2SiO2Comparative Example 15050-8515-----Example 15050-851550----Example 25050-851540----Example 35050-851530----Example 45050-8515-50---Example 55050-8515-40---Example 65050-8515--50--Example 75050-8515---50-Example 85050-8515----50Comparative Example 280-209010-----Example 980-20901050----Example 1080-20901040----Example 1180-20901030----Example 1280-209010-50---Example 1380-209010-40---Example 1480-209010-30---Example 1580-209010--50--Example 1680-209010---50-Example 1780-209010----50

[0104] 1) The content of additives is a value based on the total weight of the dianhydride compound, diamine compound, and additives. The tensile strength, tensile modulus, elongation, and density of the polyimide resins according to Examples 1 to 17 and Comparative Examples 1 and 2 were measured according to ASTM D1708. The results are shown in Table 2.

[0105] Classification Tensile strength [MPa] Tensile modulus [MPa] Elongation [%] Density [g / cm 3]Comparative Example 1160.03, 7507.001.46Embodiment 1112.86, 1882.311.86Embodiment 2112.55, 3912.731.75Embodiment 3120.84, 7213.341.69Embodiment 4102.16, 7422.132.02Embodiment 5102.15, 8212.641.81Embodiment 6132.26, 0782.782.06Embodiment 798.86, 1951.802.41Embodiment 8108.14, 5582.861.68Comparative Example 2135.04, 4304.501.47Embodiment 9106.45,1452.821.78Example 10112.54,4943.111.68Example 11131.04,0744.221.61Example 1290.55,8412.101.81Example 1395.95,7502.241.78Example 14103.15,0772.441.68Example 15118.16,2862.282.03Example 16109.85,6952.292.23Example 1792.24,5382.561.67

[0106] Among each polyimide resin, specimens with excellent tensile strength, tensile modulus, and additive dispersibility were selected, and the dimensional change rate, thermal expansion coefficient, flexural modulus, and moisture absorption rate were measured. The dimensional change rate of the polyimide resin was evaluated using specimens with Φ2.5 mm holes machined at 30 mm intervals in a molded product measuring 35 mm in width, 35 mm in length, and 5 mm in height. The dimensional change rate was evaluated by dividing the specimens into <thermal dimensional change rate>, in which they were exposed to an air atmosphere of 150 to 200°C for 3 to 5 days, and <humid dimensional change rate>, in which they were exposed to an atmosphere of 23 to 25°C and a relative humidity of 50% to 70% for 10 days.

[0107] The dimensional change rate refers to the degree of change in the distance between the holes machined in the specimen before exposure. The change in the distance between the holes was converted into a percentage to calculate the dimensional change rate. The change in the distance between the holes before and after evaluation was measured using the Bright A504 model from Mitutoyo.

[0108] The flexural modulus of each polyimide resin was measured according to ASTM D790, the coefficient of thermal expansion according to ASTM E831, and the water absorption according to ASTM D570.

[0109] The results for the dimensional change rate, flexural modulus, moisture absorption rate, and thermal expansion coefficient of the polyimide resins produced through Examples 1 to 4, Example 9, Comparative Examples 1 and 2 are shown in Table 3 below. The dimensional change rate was measured by dividing the specimens into annealed and non-annealed specimens.

[0110] Classification Heat Dimensional Change Rate [%]Humidity Dimensional Change Rate [%]Coefficient of Thermal Expansion [ppm / ℃](xy-plane)Flexural Modulus [MPa]Moisture Absorption Rate [%]Annealing × Annealing ○Annealing × Annealing ○Comparative Example 10.1020.0300.0180.01636.05,9300.070Example 10.0820.0140.0050.00517.313,4000.077Example 20.0890.0170.0130.01123.011,4500.075Example 30.0980.020 0.0160.01424.28,5400.070Example 40.0720.0150.0070.00618.613,2000.071Comparative Example 20.0510.0360.0030.00230.06,9000.033Example 90.0240.0150.0060.00618.312,2000.042

[0111] Referring to Table 3, the polyimide resins according to Examples 1 to 4 and Example 9 have a thermal dimensional change rate of 0.02% or less, a humidity dimensional change rate of 0.015% or less, a flexural modulus of 8,500 MPa or more, a thermal expansion coefficient of 25 ppm / ℃ or more, and a moisture absorption rate of 0.08% or less, thereby satisfying all conditions presented in the present invention. In addition, looking at Examples 1 to 3 and Comparative Example 1, and Example 9 and Comparative Example 2, it can be seen that the dimensional change rate, thermal expansion coefficient, and flexural modulus differ greatly depending on the presence or absence of an additive.

[0112] Meanwhile, when comparing the non-annealed specimens and the annealed specimens in Examples 1 to 4 and Example 9, it can be seen that the dimensional change rate is greatly improved when annealing is performed as in the present invention.

[0113] As a result, it was confirmed that a polyimide resin with excellent dimensional stability and high flexural modulus could be produced by selecting a monomer and a highly compatible additive, selecting an appropriate amount of input, and relieving stress through annealing.

[0114] It is expected that the polyimide resin according to the present invention can be used as a core heat-resistant component in various advanced industrial fields such as the electrical and electronic industry, automobile industry, semiconductor industry, and aerospace industry.

[0115]

[0116] The experimental examples and examples of the present invention have been described in detail above, but the scope of the present invention is not limited to the above-described experimental examples and examples, and various modifications and improvements made by those skilled in the art using the basic concept of the present invention defined in the following patent claims are also included in the scope of the present invention.

Claims

1. Contains a reactant of a diamine compound and a dianhydride compound, A polyimide resin having a thermal dimensional change rate of 0.02% or less as measured below. [Thermal dimension change rate] When a Φ2.5mm hole is machined at 30mm intervals in a molded product measuring 35mm in width, 35mm in length, and 5mm in height, and the molded product is exposed to an air atmosphere of 150℃ to 200℃ for 3 to 5 days, the rate of change in the position of the hole is measured as follows. Position change rate [%] = {(hole spacing after environmental exposure - hole spacing before environmental exposure) / (hole spacing before environmental exposure)} × 100 2. Contains a reactant of a diamine compound and a dianhydride compound, A polyimide resin having a humidity dimensional change rate of 0.015% or less as measured below. [Humidity dimension change rate] When a Φ2.5mm hole is machined at 30mm intervals in a molded product measuring 35mm in width, 35mm in length, and 5mm in height, and the molded product is exposed to an atmosphere of 23℃ to 25℃ and a relative humidity of 50% to 70% for 10 days, the rate of change in the position of the hole is measured as follows. Position change rate [%] = {(hole spacing after environmental exposure - hole spacing before environmental exposure) / (hole spacing before environmental exposure)} × 100 3. In paragraph 1 or 2, The polyimide resin further comprises at least one additive selected from the group consisting of aluminum silicate (Al2O3·2SiO2·2H2O), titanium oxide (TiO2), aluminum oxide (Al2O3), zirconium oxide (ZrO2), and combinations thereof.

4. In paragraph 3, A polyimide resin having a content of the above additive of 30% to 70% by weight.

5. In paragraph 1 or 2, A polyimide resin comprising at least one selected from the group consisting of p-phenylenediamine (p-PDA), m-phenylenediamine (m-PDA), 4,4'-oxydianiline (ODA), and combinations thereof.

6. In paragraph 1 or 2, The above diamine compound is 85 mol% to 95 mol% of p-phenylenediamine; and A polyimide resin comprising 5 mol% to 15 mol% of 4,4'-oxydianiline.

7. In paragraph 1 or 2, A polyimide resin comprising at least one selected from the group consisting of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA), 4,4'-oxydiphthalic dianhydride (ODPA), and combinations thereof.

8. In paragraph 1 or 2, The above dianhydride compound is 3,3',4,4'-biphenyltetracarboxylic acid dianhydride 30 mol% to 70 mol%; and A polyimide resin comprising 30 mol% to 70 mol% of pyromellitic acid dianhydride.

9. In paragraph 1 or 2, The above dianhydride compound is 70 mol% to 90 mol% of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride; and A polyimide resin comprising 10 mol% to 30 mol% of 4,4'-oxydiphthalic acid dianhydride.

10. In paragraph 1 or 2, A polyimide resin in which the molar ratio of the above diamine compound and the dianhydride compound is 30:70 to 70:

30.

11. In paragraph 1 or 2, The above polyimide resin is a polyimide resin having a flexural modulus of 8,500 MPa or more.

12. In paragraph 1 or 2, The above polyimide resin is a polyimide resin having a thermal expansion coefficient of 25 ppm / ℃ or less.

13. A step of preparing a starting material including a diamine compound and a dianhydride compound; A step of preparing a mixed solvent including a first solvent that is soluble in the starting material and a second solvent that is insoluble in the starting material; A step of adding the above starting materials and additives to the mixed solvent and reacting the starting materials to obtain a product; and A step of annealing the above product to obtain a polyimide resin; A method for manufacturing a polyimide resin having a thermal dimensional change rate measured according to the following of 0.02% or less or a humidity dimensional change rate measured according to the following of 0.015% or less. [Thermal dimension change rate] When a Φ2.5mm hole is machined at 30mm intervals in a molded product measuring 35mm in width, 35mm in length, and 5mm in height, and the molded product is exposed to an air atmosphere of 150℃ to 200℃ for 3 to 5 days, the rate of change in the position of the hole is measured as follows. [Humidity dimension change rate] When a Φ2.5mm hole is machined at 30mm intervals in a molded product measuring 35mm in width, 35mm in length, and 5mm in height, and the molded product is exposed to an atmosphere of 23℃ to 25℃ and a relative humidity of 50% to 70% for 10 days, the rate of change in the position of the hole is measured as follows. Position change rate [%] = {(hole spacing after environmental exposure - hole spacing before environmental exposure) / (hole spacing before environmental exposure)} × 100 14. In paragraph 13, A method for producing a polyimide resin, wherein the additive comprises at least one selected from the group consisting of aluminum silicate (Al2O3·2SiO2·2H2O), titanium oxide (TiO2), aluminum oxide (Al2O3), zirconium oxide (ZrO2), and combinations thereof.

15. In paragraph 13, The above diamine compound is 85 mol% to 95 mol% of p-phenylenediamine; and A method for producing a polyimide resin comprising 5 mol% to 15 mol% of 4,4'-oxydianiline.

16. In paragraph 13, The above dianhydride compound is 3,3',4,4'-biphenyltetracarboxylic acid dianhydride 30 mol% to 70 mol%; and A method for producing a polyimide resin comprising 30 mol% to 70 mol% of pyromellitic acid dianhydride.

17. In paragraph 13, The above dianhydride compound is 70 mol% to 90 mol% of 3,3',4,4'-biphenyltetracarboxylic acid dianhydride; and A method for producing a polyimide resin comprising 10 mol% to 30 mol% of 4,4'-oxydiphthalic acid dianhydride.

18. In paragraph 13, A method for producing a polyimide resin, wherein the molar ratio of the above diamine compound and the dianhydride compound is 30:70 to 70:

30.

19. In paragraph 13, The above polyimide resin is a method for manufacturing a polyimide resin having a flexural modulus of 8,500 MPa or more and a thermal expansion coefficient of 25 ppm / ℃ or less.

20. In paragraph 13, The step of annealing the above product to obtain a polyimide resin A method for producing a polyimide resin, comprising annealing the above product at 100°C to 300°C for 5 to 15 hours.