TW202219180A - Method for producing polyimide cured film exhibiting low dielectric loss tangent, less frequency dependence of dielectric loss tangent, and high thermal weight loss temperature - Google Patents

Abstract

This invention aims to provide a method for producing a polyimide cured film that exhibits low dielectric loss tangent, less frequency dependence of dielectric loss tangent, and high thermal weight loss temperature. The method for producing a polyimide cured film of this invention includes: (1) coating a photosensitive resin composition containing a polyimide precursor on a substrate, and forming a photosensitive resin layer on the substrate; (2) drying/heating the obtained photosensitive resin layer; (3) exposing the obtained photosensitive resin layer; (4) developing the obtained photosensitive resin layer; and (5) subjecting the photosensitive resin layer remaining on the substrate to heat treatment at 150DEG C to 250DEG C to form the cured film; the steps (2) and/or (5) are carried out at a pressure of 50 torr or more and 580 torr or less, and in the polyimide of the obtained polyimide cured film, with respect to the molecular weight of the repeating unit containing the structure derived from tetracarboxylic acid and diamine, the proportion occupied by the imide group, that is, the imide group concentration, is 12wt%-30wt%.

Description

Manufacturing method of polyimide cured film

The present invention relates to a manufacturing method of a polyimide cured film.

In the past, polyimide resins having excellent heat resistance, electrical properties and mechanical properties have been used for insulating materials of electronic parts and passivation films, surface protection films, interlayer insulating films, etc. of semiconductor devices. Among the polyimide resins, those provided in the form of photosensitive polyimide precursor compositions can be easily prepared by coating, exposing, developing, and curing-based thermal imidization of the composition. A heat-resistant uneven pattern coating is formed. This photosensitive polyimide precursor composition has the feature that the steps can be greatly reduced compared with the previous non-photosensitive polyimide materials.

In addition, a semiconductor device (hereinafter, also referred to as "element") is mounted on a printed circuit board by various methods according to the purpose. In the past, devices were usually fabricated by wire bonding in which thin metal wires were connected from the external terminals (pads) of the device to the lead frame, but recently, from the viewpoints of high-speed transmission and thinning of package height, etc. , a semiconductor chip mounting technology called fan-out wafer level packaging (FOWLP) has been proposed. The so-called FOWLP is to cut the wafer that has completed the previous steps to produce a single chip, reorganize the single chip on the support, seal it with molding resin, and peel off the support to form a rewiring layer. technology.

In recent years, it is imperative to develop packages for the 5th generation mobile communication system (5G) as a new communication standard. 5G is different from 4G of the previous technology. By using the millimeter wave (10 Gz to 80 GHz) frequency band, it can realize high-speed and large-capacity/low-latency signal/simultaneous connection of multiple terminals that did not exist in previous communications. The millimeter frequency band has a great influence on the transmission loss in the signal wiring of the printed wiring board, and there are concerns about heat generation or transmission delay. Therefore, in order to reduce transmission loss, an antenna package (AiP) has been developed by integrating a front-end module (FEM) for transmitting and receiving radio waves with an antenna (for example, refer to the following Patent Document 1). Since AiP has a short wiring length, it is possible to suppress transmission loss that increases in proportion to the wiring length. [Prior Art Literature] [Patent Literature]

[Patent Document 1] US Patent Application Publication No. 2016/0104940

[Problems to be Solved by Invention]

On the other hand, there is a limit to the suppression of transmission loss in package design, and improvement in materials is also expected. In the case where the dielectric constant or the dielectric loss tangent (tan δ) of the insulating material used to form the wiring is high, the dielectric loss increases and the transmission loss increases. In particular, although polyimide is excellent in insulating properties and film properties, since the imide group itself is a polar functional group, the value of the dielectric constant or the dielectric loss tangent is high, and the dielectric properties need to be lowered.

In view of the above technical level, the problem to be solved by the present invention is to provide a method for producing a cured polyimide film that exhibits low dielectric loss tangent, less frequency dependence of dielectric loss tangent, and higher TWD temperature , A manufacturing method of a hardened concave-convex pattern, and a polyimide cured film obtained by the method.

The inventors of the present invention have unexpectedly discovered that in the method for producing a cured polyimide film using a photosensitive resin composition containing a polyimide precursor as a raw material, by controlling the pressure during heating within a specific range, it is possible to solve the problem. The above-mentioned subject has been completed, and the present invention has been completed.

{式中，R ₂₁與R ₂₂分別獨立地為氫原子或碳數1～6之一價有機基，並且*表示連接部}。 [10]如上述[9]之再配線用層間絕緣膜形成用聚醯亞胺硬化膜，其中上述聚醯亞胺包含下述式所表示之結構中之至少1個： [化2]

{式中，*表示連接部}。 [11]如上述[9]或[10]之再配線用層間絕緣膜形成用聚醯亞胺硬化膜，其加熱至320℃時之重量減少率為0.01%～0.5%，且加熱至350℃時之重量減少率為0.1%～1.5%。 [12]一種再配線用層間絕緣膜形成用聚醯亞胺硬化膜，其加熱至320℃時之重量減少率為0.01%～0.5%，且加熱至350℃時之重量減少率為0.1%～1.5%，且藉由擾動方式分體圓柱共振器法以頻率40 GHz進行測定時之介電損耗正切為0.0021～0.0085。 [13]如上述[1]至[8]中任一項之聚醯亞胺硬化膜之製造方法，其中上述聚醯亞胺前驅物具有下述通式(1)所表示之結構： [化3]

{式中，X ₁為碳數6～40之四價有機基，Y ₁為碳數6～40之二價有機基，n ₁為2～150之整數，並且R ₁與R ₂分別獨立地為氫原子或碳數1～40之一價有機基；其中，R ₁與R ₂中之至少一者為下述通式(2)所表示之基： [化4]

(式中，R ₃、R ₄及R ₅分別獨立地為氫原子或碳數1～3之一價有機基，並且m ₁為2～10之整數)}。 [14]如上述[1]至[8]及[13]中任一項之聚醯亞胺硬化膜之製造方法，其中上述感光性樹脂組合物包含光聚合起始劑。 [15]如上述[14]之聚醯亞胺硬化膜之製造方法，其中上述通式(1)中，X ₁係下述式所表示之結構中之至少1個： [化5]

[化6]

{式中，R6係選自由氫原子、氟原子、C1～C10之烴基、及C1～C10之含氟烴基所組成之群中之一價基，l係選自0～2之整數，m係選自0～3之整數，並且n係選自0～4之整數}。 [16]如上述[13]至[15]中任一項之聚醯亞胺硬化膜之製造方法，其中上述通式(1)中，X ₁係下述式所表示之結構中之至少1個： [化7]

{式中，*表示連接部}。 [發明之效果] That is, the present invention is as follows. [1] A method for producing a polyimide cured film, characterized by comprising the following steps: (1) Coating a photosensitive resin composition comprising a polyimide precursor on a substrate, and forming a photosensitive resin composition on the substrate (2) The step of drying and heating the obtained photosensitive resin layer; (3) The step of exposing the obtained photosensitive resin layer; (4) The step of exposing the obtained photosensitive resin layer The step of developing the layer; and (5) the step of heating the photosensitive resin layer remaining on the substrate at 150°C to 250°C to form a cured film; the above steps (2) and/or (5) are in It is carried out under the pressure of 50 torr or more and 580 torr or less, and in the polyimide of the obtained polyimide cured film, with respect to the molecular weight of the repeating unit containing the structure derived from tetracarboxylic acid and diamine, amide The ratio of imine groups, that is, the concentration of imine groups, is 12 wt% to 30 wt%. [2] The method for producing a cured polyimide film according to the above [1], wherein the cured film obtained in step (5) is a dielectric at a frequency of 10 GHz obtained by a perturbation-type split cylindrical resonator method. The loss tangent is 0.001 to 0.007. [3] The method for producing a cured polyimide film according to the above [1] or [2], wherein the above step (5) is carried out under a pressure of 50 torr or more and 580 torr or less. [4] The method for producing a cured polyimide film according to the above [3], wherein in the above step (5), the temperature change from the set temperature when the set heat curing temperature is reached is 30.0°C or less. [5] The method for producing a cured polyimide film according to any one of the above [3] to [4], wherein in the region where the temperature change in the above step (5) is 9.5°C/min or less, the pressure The variation is within 150 torr. [6] The method for producing a cured polyimide film according to any one of the above [1] to [5], wherein the weight reduction rate of the obtained cured polyimide film when heated to 320° C. is 0.01% to 0.5%. [7] The method for producing a cured polyimide film according to any one of the above [1] to [6], wherein the weight reduction rate of the obtained cured polyimide film when heated to 350° C. is 0.1% to 0.1%. 1.5%. [8] The method for producing a cured polyimide film according to any one of the above [1] to [7], wherein the obtained cured polyimide film satisfies the following formula (i): 0.001<(tanδ40− tanδ10)/tanδ10＜0.2 (i) {where, tanδ40 is the dielectric loss tangent at 40 GHz obtained by the perturbation-mode split cylindrical resonator method, and tanδ10 is obtained by the perturbation-mode split cylindrical resonator method The resulting dielectric loss tangent at a frequency of 10 GHz}. [9] A cured polyimide film for forming an interlayer insulating film for rewiring, which has a dielectric loss tangent of 0.001 to 0.009 when measured at a frequency of 10 GHz by a perturbation-type split cylindrical resonator method, and the polyimide The imide has a structure represented by the following general formula (10): [Chemical 1]

{In the formula, R ₂₁ and R ₂₂ are each independently a hydrogen atom or a valent organic group having 1 to 6 carbon atoms, and * represents a linker}. [10] The cured polyimide film for forming an interlayer insulating film for rewiring according to the above [9], wherein the polyimide contains at least one of the structures represented by the following formula:

{In the formula, * represents a connecting part}. [11] The cured polyimide film for forming an interlayer insulating film for rewiring according to the above [9] or [10], which has a weight reduction rate of 0.01% to 0.5% when heated to 320° C. and heated to 350° C. The weight reduction rate is 0.1% to 1.5%. [12] A cured polyimide film for forming an interlayer insulating film for rewiring, which has a weight reduction rate of 0.01% to 0.5% when heated to 320° C., and a weight reduction rate of 0.1% to 0.1% when heated to 350° C. 1.5%, and the dielectric loss tangent is 0.0021 to 0.0085 when measured by the perturbation method split cylindrical resonator method at a frequency of 40 GHz. [13] The method for producing a cured polyimide film according to any one of the above [1] to [8], wherein the polyimide precursor has a structure represented by the following general formula (1): 3]

{In the formula, X ₁ is a tetravalent organic group with 6-40 carbon atoms, Y ₁ is a divalent organic group with 6-40 carbon atoms, n ₁ is an integer of 2-150, and R ₁ and R ₂ are each independently is a hydrogen atom or a monovalent organic group with 1 to 40 carbon atoms; wherein, at least one of R ₁ and R ₂ is a group represented by the following general formula (2):

(in the formula, R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10)}. [14] The method for producing a cured polyimide film according to any one of the above [1] to [8] and [13], wherein the photosensitive resin composition contains a photopolymerization initiator. [15] The method for producing a cured polyimide film according to the above [14], wherein in the above general formula (1), X ₁ is at least one of the structures represented by the following formula:

[hua 6]

{In the formula, R6 is a valent group selected from the group consisting of hydrogen atom, fluorine atom, hydrocarbon group of C1-C10, and fluorine-containing hydrocarbon group of C1-C10, l is an integer selected from 0-2, m is is an integer selected from 0-3, and n is an integer selected from 0-4}. [16] The method for producing a cured polyimide film according to any one of the above [13] to [15], wherein in the above general formula (1), X ₁ is at least 1 in the structure represented by the following formula each: [hua 7]

{In the formula, * represents a connecting part}. [Effect of invention]

The method for producing a cured polyimide film of the present invention heats under reduced pressure, thereby providing a polyimide with low frequency dependence of dielectric loss tangent and suppressed thermogravimetric reduction at a temperature higher than the heat curing temperature. Imide hardened film.

Hereinafter, a mode for implementing the present invention (hereinafter, abbreviated as "embodiment") will be described in detail. In addition, this invention is not limited to the following embodiment, Various changes can be carried out within the range of the summary. In the present specification, when the structures represented by the same symbols in the general formula exist in plural in the molecule, unless otherwise specified, they are independently selected, and may be the same or different from each other. In addition, unless otherwise specified, the structures represented by the common symbols in different general formulas can be selected independently, and may be the same or different from each other.

[Curing film and its manufacturing method] One embodiment of the present invention is a manufacturing method of a polyimide cured film, which is characterized by comprising the following steps: (1) the step of coating a photosensitive resin composition comprising a polyimide precursor on a substrate, and forming a photosensitive resin layer on the substrate; (2) the steps of drying and heating the obtained photosensitive resin layer; (3) the step of exposing the obtained photosensitive resin layer; (4) a step of developing the obtained photosensitive resin layer; and (5) the step of forming a cured film by heat-treating the photosensitive resin layer remaining on the substrate at 150°C to 250°C; The above-mentioned steps (2) and/or (5) are carried out under the pressure of 50 torr or more and 580 torr or less, and in the polyimide of the obtained polyimide cured film, relative to the polyimide containing tetracarboxylic acid The molecular weight of the repeating unit of the structure of the acid and the diamine, the ratio of the imino group occupied, that is, the concentration of the imino group is 12 wt% to 30 wt%. From the viewpoint of the dielectric loss tangent, the above-mentioned step (5) is preferably carried out under a pressure of 50 torr or more and 580 torr or less. The pressure is preferably 80 torr to 580 torr, preferably 100 torr to 500 torr, more preferably 120 torr to 450 torr, and still more preferably 160 torr to 420 torr. Although not bound by a specific theory, when heated at a pressure of 580 torr or less, the boiling point of the low molecular compound present in the film decreases, so it is easily vaporized and removed from the film, thereby obtaining dielectric loss in the high frequency region Reduced hardened film. At the same time, since there are few components volatilized when the cured film is heated, the weight reduction rate during heating is reduced. Also, without being bound by theory, by heating at 50 torr or more, solvent molecules are not vaporized immediately after depressurization, and imidization by heat curing is not hindered.

Hereinafter, each step will be described. [(1) The step of coating a photosensitive resin composition containing a polyimide precursor on a substrate, and forming a photosensitive resin layer on the substrate] In step (1), the photosensitive resin composition containing the polyimide precursor is coated on the substrate, and if necessary, it is then dried to form a photosensitive resin layer. As the coating method, a conventional method for coating a photosensitive resin composition, such as a spin coater, a bar coater, a knife coater, a curtain coater, a screen printing machine, can be used etc. coating method, spray coating method using a spray coater, etc.

[(2) Step of drying and heating the obtained photosensitive resin layer] In step (2), the coating film containing the photosensitive resin composition may be dried as needed. As a drying method, methods, such as air-drying, heating drying by an oven or a hot plate, and vacuum drying, are used, for example. Specifically, in the case of air-drying or heat-drying, it can be carried out at a temperature of 20°C to 140°C, more preferably 80°C to 140°C, more preferably 80°C to 120°C. The drying time can be carried out within 1 minute to 1 hour, more preferably 2 minutes to 30 minutes, more preferably 2 minutes to 10 minutes. By drying on the above-mentioned conditions, a photosensitive resin layer can be formed on a board|substrate. When performing (2) drying and heating steps by vacuum drying, the heat source is preferably selected from a heating plate or an infrared lamp. Furthermore, from the viewpoint of the heating efficiency under reduced pressure, it is preferable to place the wafer on which the coating film was formed and heat it by placing it in a heat source. (2) The drying and heating steps can be carried out under a pressure of 50 torr or more and 580 torr or less. The change in pressure from the set value is preferably within 150 torr, more preferably within 100 torr, more preferably within 80 torr, and still more preferably within 60 torr.

[(3) Step of exposing the obtained photosensitive resin layer] In step (3), exposure devices such as contact aligner, mirror projection exposure machine, stepper, etc. are used, and the above-mentioned step (1) is directly exposed to the above-mentioned step (1) through a photomask with a pattern or a main photomask by means of an ultraviolet light source, etc. The photosensitive resin layer formed in it is exposed. Thereafter, in order to improve the sensitivity, etc., post-exposure bake (PEB) and/or pre-development bake based on any combination of temperature and time may also be performed as needed. Regarding the range of the baking conditions, the temperature is preferably 40°C to 120°C, and the time is preferably 10 seconds to 240 seconds, but is not limited to this range, as long as the properties of the negative photosensitive resin composition are not impaired.

[(4) The step of developing the obtained photosensitive resin layer] In step (4), when the photosensitive resin composition is negative, the unexposed part in the photosensitive resin layer after exposure is developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any method can be selected from among known photoresist developing methods, such as spin spray method, liquid coating method, immersion method with ultrasonic treatment, etc. method to use. Moreover, after image development, in order to adjust the shape of a concave-convex pattern, etc., you may implement post-development baking at an arbitrary temperature and time combination as needed. As a developer for development, for example, a good solvent for the negative photosensitive resin composition or a combination of the good solvent and a poor solvent is preferable. As a good solvent, for example, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone, γ -Butyrolactone, α-Acetyl-γ-Butyrolactone, etc. As a poor solvent, for example, toluene, xylene, methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, water, etc. are preferable. When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of a poor solvent with respect to a good solvent by the solubility of the polymer in a negative photosensitive resin composition. Moreover, you may use 2 or more types, for example, several types of each solvent in combination.

[(5) Step of forming a cured film by heat-treating the photosensitive resin layer remaining on the substrate at 150° C. to 250° C.] In step (5) (heat hardening step), the photosensitive resin layer (concave-convex pattern) remaining on the plate obtained by the above-mentioned development is heated to disperse the photosensitive component, and (A) polyimide The precursor is imidized, thereby converting into a hardened film comprising polyimide. As the method of heating and curing, various methods, such as a method of using a hot plate, a method of using an oven, and a method of using a temperature-setting oven with a settable temperature program, can be selected, and a heating-type oven is preferable. The heating pressure in the heating oven can be performed under normal pressure (760 torr), under reduced pressure, or under increased pressure, preferably under reduced pressure (below 760 torr).

The heating and hardening step preferably includes a heating step, a constant temperature step, and a cooling step, and the constant temperature step may be performed at one temperature, or may be performed at two or more temperatures. The temperature increase step is preferably changed by 10 to 30°C in 1 minute. The heating temperature of the constant temperature step can be performed within 150°C to 250°C, preferably within 170°C to 250°C, and more preferably within 170°C to 230°C from the viewpoint of the residual film ratio before and after heating. The change of the temperature in the furnace in the constant temperature step from the set value is preferably 30.0°C or lower, more preferably 20.0°C or lower, and preferably 15.0°C or lower from the viewpoint of heating efficiency. In the constant temperature step, when the pressure is kept constant, the change of the pressure from the set value is preferably within 150 torr, more preferably within 100 torr, more preferably within 80 torr, and still more preferably within 60 torr. By keeping the pressure constant, the temperature in the furnace during the constant temperature step is stabilized. The pressure adjustment step may be performed in any step, but it is preferably performed before the temperature increase step from the viewpoint of temperature uniformity. During the pressure adjustment, the inside of the chamber may be replaced with nitrogen, and it is preferable to repeat the decompression and nitrogen replacement twice or more. The oxygen concentration inside the chamber is preferably 10 ppm or less. The cooling step is preferably changed by 10-50°C in 1 minute. The heating in the heat-hardening step can be performed under the conditions of 30 minutes to 5 hours, more preferably 1 hour to 3 hours, and more preferably 90 minutes to 3 hours. As the atmospheric gas at the time of heat-hardening, air can be used, and inert gas, such as nitrogen gas and argon gas, can also be used.

[Curing film] The obtained cured polyimide film preferably satisfies a specific dielectric loss tangent, the ratio of the peaks near 1380 cm ^-1 and near 1500 cm ^-1 in the IR (infrared radiation) spectrum meet certain values. The photosensitive resin composition used as a raw material in the manufacturing method of the polyimide cured film of the present embodiment preferably contains polyimide from the viewpoint of satisfying the following formulas (i) and/or (ii) Imine precursor: 100 parts by mass, sensitizer: 0.1 to 10 parts by mass, and solvent: 50 to 300 parts by mass, more preferably including a photoradical polymerization initiator as a sensitizer, and more preferably a photosensitive resin combination Things are negative.

<Dielectric loss tangent> The obtained cured polyimide film preferably has a dielectric loss tangent of 0.001 to 0.009, preferably 0.001 to 0.007, and further preferably 0.003～0.0065. When measuring at 28 GHz, the dielectric loss tangent is preferably 0.0021 to 0.008, more preferably 0.0030 to 0.0075, more preferably 0.0035 to 0.0075. In the case of measuring at 40 GHz, the dielectric loss tangent is preferably 0.0021 to 0.0085, more preferably 0.0030 to 0.0075, and more preferably 0.0035 to 0.0075. In the case of measuring at 60 GHz, the dielectric loss tangent is preferably 0.0021 to 0.009, more preferably 0.0030 to 0.0085, and more preferably 0.0035 to 0.0082. By setting it as this range, there exists a tendency for a signal delay etc. to be reduced when making into packages, such as AiP.

The obtained cured polyimide film preferably satisfies the following formula (i): 0.001<(tanδ ₄₀ −tanδ ₁₀ )/tanδ ₁₀ <0.2 (i) {wherein, tanδ ₄₀ is divided by a disturbance method The dielectric loss tangent at a frequency of 40 GHz obtained by the bulk cylindrical resonator method, and tanδ ₁₀ is the dielectric loss tangent at a frequency of 10 GHz obtained by the perturbation-mode split cylindrical resonator method}, and/or the following Equation (ii): 0.001＜(tanδ ₆₀ -tanδ ₁₀ )/tanδ ₁₀ ＜0.29 (ii) {where, tanδ ₆₀ is the dielectric loss tangent at 60 GHz obtained by the perturbation-mode split cylindrical resonator method , and tanδ ₁₀ is the relationship represented by the dielectric loss tangent at a frequency of 10 GHz obtained by the perturbation-mode split cylindrical resonator method. When the above equations (i) and/or (ii) are satisfied, the polarity of the cured film will be reduced, thereby reducing the dielectric loss tangent. Moreover, since the resins have good compatibility with each other, it is possible not to make the cured film before curing. The resin composition is phase-separated and stored, and the tendency of the resolution during the formation of the concave-convex pattern can be maintained.

<IR spectrum> In the IR spectrum of the obtained polyimide cured film, the ratio of the peak near 1380 cm ^-1 to the peak near 1500 cm ^-1 satisfies 0.30 to 0.54, more preferably 0.35 to 0.54, More preferably, it is 0.40-0.54, More preferably, it is 0.45-0.54. By setting the peak ratio of 1380 cm ^-1 and 1500 cm ^-1 in the IR spectrum to 0.54 or less, the polarity of the entire film can be lowered, and the increase in the dielectric loss tangent can be suppressed. On the other hand, setting the peak ratio to 0.30 or more is effective for maintaining the toughness of the resin, the adhesion to metal, and the thermal properties. In addition, the IR spectrum can be measured by the ATR-FTIR measurement apparatus shown in the following example.

＜Weight reduction rate＞ From the viewpoint of frequency dependence of dielectric loss tangent, the weight reduction rate of the obtained cured polyimide film when heated to 320°C is preferably 0.01% to 0.5%, more preferably 0.05% to 0.4%, Moreover, 0.1% - 1.5% are preferable, and, as for the weight reduction rate at the time of heating to 350 degreeC, 0.2% - 1.2% are more preferable.

[Photosensitive resin composition] The photosensitive resin composition containing the polyimide precursor contains (A) the polyimide precursor, (B) a photosensitizer, and (D) a solvent, and the photosensitive resin composition is optional Contains other ingredients. Each component will be described in order below.

{式中，X ₁為碳數6～40之四價有機基，Y ₁為碳數6～40之二價有機基，n ₁為2～150之整數，並且R ₁與R ₂分別獨立地為氫原子或碳數1～40之一價有機基；其中，R ₁與R ₂中之至少一個為下述通式(2)所表示之基： [化9]

(式中，R ₃、R ₄及R ₅分別獨立地為氫原子或碳數1～3之一價有機基，並且m ₁為2～10之整數)}。 The photosensitive resin composition can be either negative type or positive type according to the desired application, and from the viewpoint of the physical properties of the following (A) polyimide precursor, the negative type (A) polyimide precursor is preferred. Imide Precursor The polyimide precursor is a resin component contained in the photosensitive resin composition, preferably a polyimide having a structural unit represented by the following general formula (1):

{In the formula, X ₁ is a tetravalent organic group with 6-40 carbon atoms, Y ₁ is a divalent organic group with 6-40 carbon atoms, n ₁ is an integer of 2-150, and R ₁ and R ₂ are each independently is a hydrogen atom or a monovalent organic group with 1 to 40 carbon atoms; wherein, at least one of R ₁ and R ₂ is a group represented by the following general formula (2):

(in the formula, R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10)}.

From the viewpoint of high resolution, the valent organic group represented by the general formula (2) contained in the polyimide precursor is relative to all R ₁ and R of the precursor represented by the general formula (1) above. The ratio of ₂ is preferably 50 mol % to 100 mol %, and more preferably 75 mol % to 100 mol % from the viewpoint of high chemical resistance and sensitivity.

From the viewpoint of the photosensitive properties and mechanical properties of the photosensitive resin composition, n1 in the general formula (1) is preferably an integer of 3-100, more preferably an integer of 5-70.

[化11]

{式(20)中，R6係選自由氫原子、氟原子、C1～C10之烴基、及C1～C10之含氟烴基所組成之群中之一價基，l係選自0～2之整數，m係選自0～3之整數，並且n係選自0～4之整數}，但並不限定於該等。又，X ₁之結構可為1種，亦可為2種以上之組合。就兼顧耐熱性與感光特性之方面而言，尤佳為具有上述式(20)所表示之結構之X ₁基。 In the above general formula (1), in terms of both heat resistance and photosensitivity, the tetravalent organic group represented by X ₁ is preferably an organic group having 6 to 40 carbon atoms, more preferably a -COOR ₁ group and - An aromatic group or an alicyclic aliphatic group in which the COOR ₂ group and the -CONH- group are located in ortho positions to each other. Specific examples of the tetravalent organic group represented by X ₁ include organic groups having 6 to 40 carbon atoms in an aromatic ring, for example, groups having a structure represented by the following general formula (20): [ 10]

[Chemical 11]

{In formula (20), R6 is a valent group selected from the group consisting of a hydrogen atom, a fluorine atom, a hydrocarbon group of C1-C10, and a fluorine-containing hydrocarbon group of C1-C10, and l is an integer selected from 0-2 , m is an integer selected from 0-3, and n is an integer selected from 0-4}, but not limited to these. In addition, the structure of X ₁ may be one type or a combination of two or more types. The X ₁ group having the structure represented by the above formula (20) is particularly preferable in terms of both heat resistance and photosensitivity.

{式中，Ry分別獨立地表示可包含鹵素原子之碳數1～10之一價有機基，a表示0～4之整數，C為氧原子或硫原子，並且D為單鍵或下述式所表示之至少1種基： [化13]

}， 其中，尤佳為下述式： [化14]

或下述式： [化15]

所表示之結構。 As the structure represented by X1, from the viewpoint _of low dielectric loss tangent, among the structures represented by the above formula (20), the structure represented by the following formula (X1) is particularly preferred:

{in the formula, Ry each independently represents a C1-10 valent organic group which may contain a halogen atom, a represents an integer of 0-4, C is an oxygen atom or a sulfur atom, and D is a single bond or the following formula Represented at least one kind of base: [Chem. 13]

}, wherein, the following formula is particularly preferred: [Chem. 14]

Or the following formula: [Chem.15]

represented structure.

The structure represented by X ₁ is preferably a structure represented by the following formula from the viewpoint of the thermal weight reduction rate:

[化18]

{式(21)中，R6係選自由氫原子、氟原子、C1～C10之烴基、及C1～C10之含氟烴基所組成之群中之一價基，m係選自0～3之整數，並且n係選自0～4之整數}，但並不限定於該等。又，Y ₁之結構可為1種，亦可為2種以上之組合。就兼顧耐熱性及感光特性之方面而言，尤佳為藉由上述式(21)所表示之結構之Y ₁基。 In the general formula (1), the divalent organic group represented by Y ₁ is preferably an aromatic group having 6 to 40 carbon atoms in terms of both heat resistance and photosensitivity. For example, the following formula ( 21) The structure represented: [化17]

[Chemical 18]

{In formula (21), R6 is a valent group selected from the group consisting of hydrogen atom, fluorine atom, hydrocarbon group of C1-C10, and fluorine-containing hydrocarbon group of C1-C10, m is an integer selected from 0-3 , and n is an integer selected from 0 to 4}, but is not limited to these. In addition, the structure of Y ₁ may be 1 type or a combination of 2 or more types may be sufficient as it. The Y ₁ group of the structure represented by the above formula (21) is particularly preferable in terms of both heat resistance and photosensitivity characteristics.

{式中，Rz分別獨立地為可包含鹵素原子之碳數1～10之一價有機基，a為0～4之整數，A為氧原子或硫原子，並且B為單鍵或下述式所表示之至少1種基： [化20]

}， 就低介電損耗正切、低介電常數、平版印刷性之觀點而言，進而較佳為下述式： [化21]

或下述式： [化22]

或下述式： [化23]

所表示之結構。 As the Y ₁ group, from the viewpoint of reducing the dielectric loss tangent, among the structures represented by the above formula (21), a structure represented by the following formula (Y1) is particularly preferred: [Chemical 19]

{wherein, Rz is each independently a C1-10 monovalent organic group which may contain a halogen atom, a is an integer of 0-4, A is an oxygen atom or a sulfur atom, and B is a single bond or the following formula Represented at least one kind of base: [Chem. 20]

}, From the viewpoint of low dielectric loss tangent, low dielectric constant, and lithographic printability, it is more preferably the following formula: [Chem. 21]

Or the following formula: [Chemical 22]

Or the following formula: [Chemical 23]

represented structure.

R ₃ in the above general formula (2) is preferably a hydrogen atom or a methyl group, and from the viewpoint of photosensitive properties, R ₄ and R ₅ are preferably a hydrogen atom. Moreover, m ₁ is an integer of 2 or more and 10 or less, and preferably an integer of 2 or more and 4 or less, from the viewpoint of photosensitive properties.

In this specification, the term "imide group concentration" refers to the polyimide of the cured polyimide film obtained by heating and curing the photosensitive resin composition of the present embodiment, relative to the polyimide containing The molecular weight of the repeating unit of the structure of carboxylic acid and diamine, and the ratio of the mass occupied by the imide group. In this embodiment, the concentration of imide groups in the obtained polyimide cured film is 12 wt % to 30 wt %, preferably 12 wt % to 24 wt %. When the imide group concentration is 12 wt % or more, the adhesion between the mold resin and the hardened uneven pattern tends to be good. The imide group concentration is preferably 12.5 wt% or more, more preferably 13.5 wt% or more. On the other hand, there exists a tendency for the dielectric loss tangent of the polyimide cured film obtained to be favorable by making the imide group concentration 30 wt % or less. The imide group concentration is preferably 24.0 wt% or less, more preferably 23.0 wt% or less, and still more preferably 21.0 wt% or less.

The concentration of imide groups in each repeating unit of polyimide is the molecular weight of the tetracarboxylic acid and diamine used in the preparation of the polyimide precursor, and is represented by the following formula (I): 70.02 ×2/[Mw(A)+Mw(B)]×100 (I) {In formula (I), Mw(A) represents the molecular weight of tetracarboxylic acid, and Mw(B) represents the molecular weight of diamine}. In addition, when using two or more types of tetracarboxylic acids and/or diamines, for example, when preparing using two types of tetracarboxylic acids and/or diamines, it is represented by the following formula (II) : 70.02×2/[Mw(A1)×a ₁ +Mw(A2)×a ₂ +Mw(B1)×b ₁ +Mw(B2)×b ₂ ]×100 (II) {In formula (II), Mw(A1) ) represents the molecular weight of the first tetracarboxylic acid, Mw(A2) represents the molecular weight of the second tetracarboxylic acid, a ₁ represents the content of the first tetracarboxylic acid, a ₂ represents the content of the second tetracarboxylic acid, and Mw(B1) represents the The molecular weight of the first diamine, Mw(B2) represents the molecular weight of the second diamine, b ₁ represents the content of the first diamine, and b ₂ represents the content of the second diamine; wherein, a ₁ , a ₂ , b ₁ , b ₂ respectively satisfy a ₁ +a ₂ =1, b ₁ +b ₂ =1}. When three or more types of tetracarboxylic acids and/or diamines are used, it is determined in the same manner. When tetracarboxylic dianhydride is used as a raw material, it calculates after converting into tetracarboxylic acid.

(A) Preparation method of polyimide precursor The polyimide precursor including the structure represented by the general formula (1) is obtained, for example, by a method including: Tetravalent organic group X ₁ tetracarboxylic dianhydride and (a) alcohols having a structure in which a valent organic group represented by the above general formula (2) is bonded to a hydroxyl group, and optionally (b) having the above general formula (2) The alcohols of the structure other than the group represented by the formula (2) are reacted to prepare partially esterified tetracarboxylic acid (hereinafter, also referred to as acid/ester body); Diamine polycondensation of divalent organic group Y ₁ with 6 to 40 carbon atoms.

(Preparation of acid/ester body) As tetracarboxylic dianhydride containing tetravalent organic group X ₁ of carbon number 6 to 40, for example, pyromellitic dianhydride, diphenyl ether-3,3', 4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride , diphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3, 4-phthalic anhydride) propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, 4,4'-(4 , 4'-isopropylidene diphenoxy) acid dianhydride and the like. Moreover, these can be used individually by 1 type, or in mixture of 2 or more types.

Examples of (b) alcohols having a structure other than the group represented by the general formula (2) include aliphatic alcohols having 5 to 30 carbon atoms or aromatic alcohols having 6 to 30 carbon atoms, such as 1-pentane. Alcohol, 2-pentanol, 3-pentanol, neopentanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol , triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, benzyl alcohol, etc.

The desired acid can be obtained by dissolving and mixing the above-mentioned tetracarboxylic dianhydride and the above-mentioned alcohols (a) in a reaction solvent in the presence of a basic catalyst such as pyridine, thereby carrying out the half-esterification reaction of the acid dianhydride. /ester body. The reaction conditions are preferably stirring at a reaction temperature of 20 to 50° C. for 4 to 10 hours.

The reaction solvent is preferably one that dissolves the acid/ester body and a polyimide precursor that is a polycondensation product of the acid/ester body and diamines. Examples of the reaction solvent include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, and tetramethylurea. , γ-butyrolactone, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, Ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane alkane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene, etc. These may be used individually as needed, and may be used in mixture of 2 or more types.

(Preparation of Polyimide Precursor) In the above acid/ester body (typically a solution in the above reaction solvent), a known dehydration condensing agent is mixed under ice-cooling to form the acid/ester body into a polyanhydride. , a polyimide precursor can be obtained by adding dropwise thereto and separately dissolving or dispersing diamines containing a divalent organic group Y ₁ of carbon number 6 to 40 in a solvent and performing polycondensation. As the dehydration condensing agent, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy- Di-1,2,3-benzotriazole, N,N'-dibutadiimide carbonate, etc.

As diamines containing a divalent organic group Y ₁ having 6 to 40 carbon atoms, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4' can also be mentioned. -Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3' -Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4, 4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobiphenyl Aminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diphenylmethane Aminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy) base) benzene, bis[4-(4-aminophenoxy)phenyl]sine, bis[4-(3-aminophenoxy)phenyl]sine, 4,4-bis(4-amino) phenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-amine) phenoxy)phenyl] ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)benzene Phenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenyl) Phenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl) ) benzene, o-tolidine, 9,9-bis(4-aminophenoxy)phenyl, 2,2-bis{3-methyl-4-(4-aminophenoxy)phenyl} Propane, bis{4-(4-aminophenoxy)phenyl}ketone, and a portion of the hydrogen atoms on the benzene ring of these are substituted with methyl, ethyl, hydroxymethyl, hydroxyethyl, halogen etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl Methyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4' - Diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, mixtures of these, etc. However, the diamines are not limited to these.

In order to improve the adhesiveness between the photosensitive resin layer formed on the substrate and various substrates by applying the photosensitive resin composition on the substrate, in the preparation of the (A) polyimide precursor, it is also possible to Diaminosiloxanes such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(3-aminopropyl)tetraphenyldisiloxane, etc. Copolymerization.

After the above-mentioned polycondensation reaction is finished, the water-absorbing by-products of the coexisting dehydration condensing agent in the reaction solution can also be filtered and separated as needed, and then poor solvents such as water, aliphatic lower alcohols or their mixed solutions are put into the reaction solution to polymerize. Composition analysis. Furthermore, the polymer can also be purified by repeating the above-mentioned redissolving and reprecipitation precipitation operations. Next, the polymer can be vacuum dried to isolate the polyimide precursor. In order to improve the degree of refinement, the solution of the polymer can also be used to swell an anion and/or cation exchange resin with an appropriate organic solvent and then fill a column to remove ionic impurities.

When the molecular weight of the (A) polyimide precursor is measured by the polystyrene conversion weight average molecular weight obtained by gel permeation chromatography, it is preferably 8,000-150,000, more preferably 9,000- 50,000, preferably 18,000 to 40,000. When the weight average molecular weight is 8,000 or more, the mechanical properties are good, which is preferable. On the other hand, when the weight average molecular weight is 150,000 or less, the dispersibility to the developer and the resolution performance of the concavo-convex pattern are good, which is preferable. As a developing solvent for gel permeation chromatography, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, the molecular weight was calculated|required from the calibration curve produced using the standard monodisperse polystyrene. As a standard monodisperse polystyrene, it is recommended to select STANDARD SM-105, an organic solvent-based standard sample manufactured by Showa Denko Co., Ltd.

、2-甲基9-氧硫𠮿

、2-異丙基9-氧硫𠮿

、二乙基9-氧硫𠮿

等9-氧硫𠮿

衍生物；苯偶醯、苯偶醯二甲基縮酮、苯偶醯-β-甲氧基乙基縮醛等苯偶醯衍生物；安息香、安息香甲醚等安息香衍生物；1-苯基-1,2-丁二酮-2-(鄰甲氧基羰基)肟、1-苯基-1,2-丙二酮-2-(鄰甲氧基羰基)肟、1-苯基-1,2-丙二酮-2-(鄰乙氧基羰基)肟、1-苯基-1,2-丙二酮-2-(鄰苯甲醯基)肟、1,3-二苯基丙三酮-2-(鄰乙氧基羰基)肟、1-苯基-3-乙氧基丙三酮-2-(鄰苯甲醯基)肟等肟類；N-苯基甘胺酸等N-芳基甘胺酸類；過氯化苯甲醯等過氧化物類；芳香族聯咪唑類、二茂鈦類、α-(正辛磺醯氧基亞胺基)-4-甲氧基苄基氰化物等光酸產生劑類等；但並不限定於該等。於上述光聚合起始劑之中，尤其是就感光度之方面而言，更佳為肟類。(B) Sensitizer The photosensitive resin composition contains a sensitizer. In one embodiment, the photosensitizer can also be a photopolymerization initiator. The photopolymerization initiator is preferable because it promotes hardening of the concavo-convex pattern by light irradiation. The photopolymerization initiator is preferably a photoradical polymerization initiator, and examples include benzophenone, methyl o-benzoic acid benzoate, and 4-benzyl-4'-methyl. Benzophenone derivatives such as benzophenone, dibenzyl ketone, and fenone; 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl Acetophenone derivatives such as phenyl ketone; 9-oxosulfur

, 2-methyl 9-oxothio

, 2-isopropyl 9-oxothio

, diethyl 9-oxothio

Wait for 9-oxysulfur 𠮿

Derivatives; benzil derivatives such as benzil, benzil dimethyl ketal, benzil-β-methoxyethyl acetal, etc.; benzoin derivatives such as benzoin and benzoin methyl ether; 1-phenyl -1,2-Butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1 ,2-Propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzyl)oxime, 1,3-diphenylpropane Oximes such as triketo-2-(o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxyglycerol-2-(o-benzyl) oxime; N-phenylglycine, etc. N-arylglycines; peroxides such as benzalkonium chloride; aromatic biimidazoles, titanocenes, α-(n-octanesulfonyloxyimino)-4-methoxy Photoacid generators such as benzyl cyanide, etc.; but not limited to these. Among the above-mentioned photopolymerization initiators, oximes are more preferred in terms of sensitivity.

The compounding amount of the photopolymerization initiator is preferably 0.1 part by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the (A) polyimide precursor. The said compounding quantity is 0.1 mass part or more from a viewpoint of sensitivity or patternability, and 10 mass parts or less is preferable from a viewpoint of the physical property of the photosensitive resin layer after hardening of the photosensitive resin composition.

(C) Solvent (Solvent) The photosensitive resin composition of this embodiment contains a solvent. As a solvent, it is preferable to use a polar organic solvent from the point of solubility with respect to the (A) polyimide precursor. Specific examples of the solvent include N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylformamide Ethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetoxy-γ-butyrolactone, tetramethylurea, 1,3- Dimethyl-2-imidazolidinone, N-cyclohexyl-2-pyrrolidone, 2-octanone, etc.; these can be used alone or in combination of two or more.

The above-mentioned solvent corresponds to the required coating film thickness and viscosity of the photosensitive resin composition, and can be, for example, 50 parts by mass to 300 parts by mass, preferably 100 parts by mass relative to 100 parts by mass of the (A) polyimide precursor. part to 300 parts by mass.

From the viewpoint of improving the storage stability of the photosensitive resin composition, a solvent containing alcohols is preferred. The alcohols that can be preferably used are typically alcohols having an alcoholic hydroxyl group in the molecule and no olefinic double bond, and specific examples include methanol, ethanol, n-propanol, isopropanol, n-butyl alcohol. Alkanols such as alcohol, isobutanol, tert-butanol; lactate esters such as ethyl lactate; propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, propylene glycol -1-(n-propyl) ether, propylene glycol-2-(n-propyl) ether and other propylene glycol monoalkyl ethers; ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether and other monoalcohols ; 2-hydroxyisobutyrate; glycols such as ethylene glycol and propylene glycol. Among these, lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyric acid esters, and ethanol are preferable, and ethyl lactate, propylene glycol-1-methyl ether, and propylene glycol-1-methyl ether are particularly preferable. ether, and propylene glycol-1-(n-propyl) ether.

When the solvent contains an alcohol without olefinic double bonds, taking the mass of the total solvent as a reference, the content of the alcohol without olefinic double bonds in the total solvent is preferably 5% by mass to 50% by mass, more preferably It is 10 mass % - 30 mass %. When the said content of the alcohol which does not have an olefinic double bond is 5 mass % or more, the storage stability of the photosensitive resin composition becomes favorable, and on the other hand, when it is 50 mass % or less, (A) The solubility of the polyimide precursor becomes good.

[Other components] The photosensitive resin composition may further contain components other than the above-mentioned (A), (B), and (C) components. Examples of other components include: (A) resin components other than polyimide precursors; sensitizers; monomers having photopolymerizable unsaturated bonds; adjuvants; thermal polymerization inhibitors; azole compounds; and hindered phenolic compounds.

The photosensitive resin composition may further contain resin components other than the (A) polyimide precursor. As the resin component which can be contained in the photosensitive resin composition, for example, polyimide, polyoxazole, polyoxazole precursor, phenolic resin, polyamide, epoxy resin, and siloxane resin may be mentioned. , acrylic resin, etc. It is preferable that the compounding quantity of these resin components is the range of 0.01-20 mass parts with respect to 100 mass parts of (A) polyimide precursors.

When using (A) the polyimide precursor and the polyoxazole precursor together to prepare the positive photosensitive resin composition, as the positive photosensitive material, a compound having a quinonediazide group such as Compounds having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure are used in combination.

In order to improve the sensitivity, the photosensitive resin composition may optionally contain a sensitizer. As this sensitizer, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene) may, for example, be mentioned. base) cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4 -Methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnylene , p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenyl biphenylene)-benzothiazole, 2-(p-dimethylaminophenyl vinylidene) benzothiazole , 2-(p-dimethylaminophenylvinylidene) isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'- Diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-Ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylamino Coumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N -Phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5 -Mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-( p-Dimethylaminostyryl) naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, etc. These can be used alone or in combination of plural kinds (for example, 2 to 5 kinds). The compounding amount of the sensitizer is preferably 0.1 to 25 parts by mass relative to 100 parts by mass of the (A) polyimide precursor.

The compounding amount of the sensitizer is preferably 0.1 to 25 parts by mass relative to 100 parts by mass of the (A) polyimide precursor.

In order to improve the resolution of the uneven pattern, the photosensitive resin composition may optionally contain a monomer having a photopolymerizable unsaturated bond. Such a monomer is preferably a (meth)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator, and is not particularly limited to the following. Examples of such monomers include diethylene glycol dimethacrylate, tetrakis Ethylene glycol dimethacrylate represented by ethylene glycol or polyethylene glycol mono or diacrylate or methacrylate, propylene glycol or polypropylene glycol mono or diacrylate or methacrylate, glycerol mono , di- or triacrylate or methacrylate, cyclohexane diacrylate or dimethacrylate, 1,4-butanediol diacrylate or dimethacrylate, 1,6-hexanediol Diacrylate or dimethacrylate of neopentyl glycol, diacrylate or dimethacrylate of neopentyl glycol, mono- or diacrylate or methacrylate of bisphenol A, benzene trimethacrylate, isoacrylate Ester or methacrylate, acrylamide, its derivatives, methacrylamide, its derivatives, trimethylolpropane triacrylate or methacrylate, glycerol di- or triacrylate or methyl methacrylate Acrylates, di-, tri- or tetra-acrylates or methacrylates of pentaerythritol, ethylene oxide or propylene oxide adducts of these compounds and other compounds. In addition, these monomers may be used 1 type, and may be used as a mixture of 2 or more types.

It is preferable that the compounding quantity of the monomer which has a photopolymerizable unsaturated bond is 1-50 mass parts with respect to 100 mass parts of (A) polyimide precursors.

In order to improve the adhesiveness of the film formed using the photosensitive resin composition, and a base material, the photosensitive resin composition may contain an adhesive adjuvant arbitrarily. As the adhesive agent, for example, γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-shrinkage Glyceryloxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloyloxypropyldimethoxymethylsilane, 3-methacryloyl Oxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinylpropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxy methylsilylpropyl) butadiimide, N-[3-(triethoxysilyl)propyl]phthalic acid, benzophenone-3,3'-bis( N-[3-Triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, Benzene-1,4-bis(N-[3-triethoxysilyl]propylamide) amine)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, silane coupling agents such as N-phenylaminopropyltrimethoxysilane, and tris(ethyl ethyl acetate) Aluminium-based adhering aids such as aluminium acetoacetate and aluminium tris(acetylacetonate), etc. In addition, these adhesive adjuvants may be used alone or as a mixture of two or more.

Among these adhesive agents, it is more preferable to use a silane coupling agent in terms of adhesive force. The blending amount of the adjuvant is preferably in the range of 0.5 parts by mass to 25 parts by mass relative to 100 parts by mass of the (A) polyimide precursor.

The photosensitive resin composition may optionally contain a thermal polymerization inhibitor in order to improve the viscosity of the photosensitive resin composition and the stability of the photosensitivity especially when stored in the state of a solution containing a solvent. As the thermal polymerization inhibitor, for example, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetramine are used. Acetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1-Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso ammonium-N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, etc. In addition, these thermal polymerization inhibitors may be used by 1 type, and may be used as a mixture of 2 or more types.

As a compounding quantity of a thermal polymerization inhibitor, the range of 0.005 mass part - 12 mass parts is preferable with respect to 100 mass parts of (A) polyimide precursors.

For example, in the case of using a substrate containing copper or a copper alloy, the photosensitive resin composition may optionally contain an azole compound in order to suppress discoloration of the substrate. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, and 5-benzene base-1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5 -Phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5- Diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α, α-Dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl) yl-5-methyl-2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'- hydroxy-5'-tert-octylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzene Triazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole , 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, etc. Particularly preferred examples thereof include tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. In addition, these azole compounds may be used 1 type, and may be used as a mixture of 2 or more types.

The compounding amount of the azole compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) polyimide precursor, and more preferably 0.5 to 5 parts by mass from the viewpoint of sensitivity characteristics . If the compounding amount of the azole compound with respect to 100 parts by mass of the polyimide precursor (A) is 0.1 part by mass or more, when the photosensitive resin composition is formed on copper or copper alloy, the surface of copper or copper alloy is discolored. On the other hand, if it is 20 parts by mass or less, since the sensitivity is excellent, it is preferable.

In order to suppress discoloration of copper, the photosensitive resin composition may contain a hindered phenol compound. Examples of hindered phenol compounds include 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, 3-(3,5- Di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4 '-Methylenebis(2,6-di-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-Butylene Base-bis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] , 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-dieneethylbis[3 -(3,5-Di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy- phenylalanamide), 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol) tributylphenol), pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-tert-butyl- 4-Hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene , 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-tris-2,4,6-(1H,3H, 5H)-trione, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris𠯤-2,4,6 -(1H,3H,5H)-trione, 1,3,5-tris(4-second-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris𠯤 -2,4,6-(1H,3H,5H)-trione, 1,3,5-tri[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl ]-1,3,5-Tris𠯤-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2, 6-Dimethylbenzyl]-1,3,5-tris𠯤-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6 -Dimethyl-4-phenylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-th Tributyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3 ,5-Tris(4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H, 3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3 ,5-Tris𠯤-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2,5 -Dimethylbenzyl)-1,3,5-tri(2,4,6-(1H,3H,5H)-trione, 1,3,5-tri(4-tert-butyl-5) ,6-Diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6-(1H,3H,5H)-trione, 1,3,5 -Tris(4-tert-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris𠯤-2,4,6-(1H,3H,5H)-trione, 1, 3,5-Tris(4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-tris𠯤-2,4,6-(1H,3H,5H) -Triketone, 1,3,5-tris(4-tert-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-tris-2,4,6 -(1H,3H,5H)-triketone, etc.; but not limited thereto. Among these, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4 is particularly preferred ,6-(1H,3H,5H)-trione.

The blending amount of the hindered phenol compound is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the (A) polyimide precursor, and more preferably 0.5 to 10 parts by mass from the viewpoint of sensitivity characteristics share. If the blending amount of the hindered phenol compound is 0.1 part by mass or more with respect to 100 parts by mass of the (A) polyimide precursor, for example, when the photosensitive resin composition is formed on copper or copper alloy, copper or Discoloration and corrosion of the copper alloy are prevented, but on the other hand, if it is 20 parts by mass or less, since the sensitivity is excellent, it is preferable.

An organic compound containing a metal element selected from titanium or zirconium may be contained in the photosensitive resin composition. It is preferable that the said organic compound contains 1 type of metal element chosen from titanium and zirconium in one molecule. As the organic group, a hydrocarbon group including a hydrocarbon group and a hydrocarbon group including a hetero atom are preferable. By containing the above-mentioned organic compound, the imidization rate of the photosensitive resin composition increases, and the dielectric loss tangent of the cured film decreases.

As the organic titanium or zirconium compound that can be used, for example, an organic chemical substance is bonded to a titanium or zirconium atom via a covalent bond or an ionic bond.

Specific examples of organotitanium or zirconium compounds are shown in the following I) to VII): As I) a chelate compound, it is more preferable that it is a compound which has 2 or more alkoxy groups from the viewpoint of the storage stability of the photosensitive resin composition and a favorable pattern. Specific examples of the chelate compound include titanium bis(triethanolamine)diisopropoxide, titanium bis(2,4-glutaric acid)di-n-butoxide, bis(2,4-glutaric acid)di Titanium isopropoxide, titanium bis(tetramethylpimelate) diisopropoxide, titanium diisopropoxide bis(ethyl acetate), and compounds in which the titanium atom of these compounds is replaced by a zirconium atom; but Not limited to these.

As the II) tetraalkoxy compound, titanium tetra-n-butoxide, titanium tetraethoxide, titanium tetrakis(2-ethylhexanoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide may, for example, be mentioned. , titanium tetramethoxypropoxide, titanium tetramethylphenolate, titanium tetra-n-nonoxide, titanium tetra-n-propoxide, titanium tetrastearyloxide, tetrakis[bis{2,2-(allyloxymethyl)butane] Alcohol}] titanium, compounds in which the titanium atoms of these compounds are substituted with zirconium atoms; but are not limited to these.

As III) titanocene or zirconocene compound, for example, pentamethylcyclopentadienyl titanium trimethoxide, bis(η ⁵ -2,4-cyclopentadien-1-yl)bis(2 ,6-difluorophenyl) titanium, bis(n ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl ) Titanium, compounds in which the titanium atoms of these compounds are replaced by zirconium atoms; but are not limited to these.

Examples of IV) monoalkoxy compounds include titanium tris(dioctylsulfonate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, and titanium atoms of these compounds are substituted It is a compound of zirconium atom; but it is not limited to these.

As V) oxytitanium or oxyzirconium compounds, for example, bis(glutaric acid) oxytitanium, bis(tetramethylpimelic acid) oxytitanium, phthalocyanine oxytitanium, and the titanium atoms of these compounds are substituted with Compounds of zirconium atoms; but not limited to these.

As VI) tetraacetylacetonate titanium or tetraacetylacetonate zirconium compounds, for example, can be exemplified: tetraacetylacetonate titanium, the compounds whose titanium atoms are substituted with zirconium atoms; but not limited to these compounds. Wait.

As VII) titanate coupling agent, tris (dodecylbenzenesulfonyl) isopropyl titanate etc. are mentioned, for example, However, It is not limited to these.

Among the above I) to VII), from the viewpoint of achieving a better dielectric loss tangent, the organic titanium compound is preferably selected from the above I) titanium chelate compound, II) tetraalkoxy titanium compound, and III) At least one compound in the group consisting of titanocene compounds. Especially preferred are titanium diisopropoxide bis(ethyl acetate), titanium tetra-n-butoxide, and bis(n ⁵ -2,4-cyclopentadien-1-yl)bis(2,6-difluoro) -3-(1H-pyrrol-1-yl)phenyl)titanium.

When blending the organic titanium or zirconium compound, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the resin (A). If the compounding amount is 0.05 parts by mass or more, the imidization rate of the photosensitive resin composition and the dielectric loss tangent of the cured film will be favorable, and on the other hand, if it is 10 parts by mass or less, the photosensitive The resin composition is preferable because of its excellent storage stability.

{通式(11)中，X ¹及Y ¹與通式(1)中之X ₁及Y ₁相同，並且m為正整數}。 通式(1)中之較佳之X ₁與Y ₁因相同原因，於通式(11)所表示之聚醯亞胺中亦較佳。通式(11)之重複單元數m並無特別限定，亦可為2～150之整數。 [Polyimide] The structure of the polyimide contained in the cured uneven pattern (polyimide cured film) formed from the above-mentioned polyimide precursor composition is preferably the following general formula (11) Represented: [化24]

{In the general formula (11), X ¹ and Y ¹ are the same as X ₁ and Y ₁ in the general formula (1), and m is a positive integer}. Preferred X ₁ and Y ₁ in the general formula (1) are also preferred in the polyimide represented by the general formula (11) for the same reason. The number m of repeating units of the general formula (11) is not particularly limited, and may be an integer of 2 to 150.

Another embodiment of the present invention is the polyimide cured film itself for forming an interlayer insulating film for rewiring, and the weight reduction rate when heated to 320°C is 0.01% to 0.5%, and the weight reduction rate when heated to 350°C It is 0.1% to 1.5%, and the dielectric loss tangent is 0.0021 to 0.0085 when measured by the perturbation method split cylindrical resonator method at a frequency of 40 GHz.

[Semiconductor Device] Another embodiment of the present invention is also a semiconductor device having a hardened concavo-convex pattern obtained by the above-mentioned method for producing a hardened concavo-convex pattern, that is, a semiconductor device having a substrate as a semiconductor element, and a semiconductor device having a hardened concavo-convex pattern. The above-mentioned method for producing a hardened concavo-convex pattern forms a semiconductor device of a polyimide hardened concavo-convex pattern on the substrate. Moreover, the manufacturing method of the polyimide cured film of this invention can also be applied to the manufacturing method of the semiconductor device which uses a semiconductor element as a base material and contains the manufacturing method of the said hardening uneven|corrugated pattern as a part of a process. The semiconductor device of the present embodiment can be manufactured by forming the hardened concavo-convex pattern formed by the above-mentioned method for producing a hardened concavo-convex pattern as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for flip-chip devices, a A protective film of a semiconductor device with a bump structure, etc., is combined with a known manufacturing method of a semiconductor device.

[Display Device] Another embodiment of the present invention is also a display device, which includes a display element and a cured film disposed on the upper portion of the display element, and the cured film is the above-mentioned cured concave-convex pattern. Here, the hardened concavo-convex pattern may be directly laminated with the display element, or may be laminated through other laminated layers. For example, as this cured film, the surface protection film of TFT (Thin Film Transistor, thin film transistor) liquid crystal display element and color filter element, insulating film, planarization film, MVA (Multi-Domain Vertical Alignment, Multi-domain vertical alignment) type liquid crystal display device for protrusions, organic EL (Electroluminescence, electroluminescence) element cathode for the partition wall.

The manufacturing method of the polyimide cured film of the present invention can be applied not only to the above-mentioned semiconductor devices, but also to the interlayer insulation of multilayer circuits, the hard coating of flexible copper clad laminates, solder resist films, and liquid crystal alignment films. and other uses. [Example]

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to an Example. In Examples, Comparative Examples, and Production Examples, various physical properties and the like were measured and evaluated using the following measurement and evaluation methods.

[Measurement and evaluation method] (1) Weight average molecular weight The weight average molecular weight (Mw) of each resin was measured by gel permeation chromatography (standard polystyrene conversion). The column used for the measurement is the trade name "Shodex 805M/806M series" manufactured by Showa Denko Co., Ltd., the standard monodisperse polystyrene is the trade name "Shodex STANDARD SM-105" manufactured by Showa Denko Co., Ltd., and the developing solvent As N-methyl-2-pyrrolidone, the detector used the trade name "Shodex RI-930" manufactured by Showa Denko Co., Ltd.

(2) The dielectric constant (Dk) and the dielectric loss tangent (Df) were measured using a sputtering apparatus (model L-440S-FHL, manufactured by CANON ANELVA) on a 6-inch silicon wafer (Fujimi Electronics Co., Ltd. Manufacture, sputtering aluminum (Al) with a thickness of 100 nm on a thickness of 625±25 μm) to prepare an Al wafer substrate for sputtering. The negative photosensitive resin composition was spin-coated on the above-mentioned sputtered Al wafer substrate using a spin coater (model D-spin60A, manufactured by SOKUDO), and heated and dried at 110° C. for 3 minutes to prepare a spin-coated film. Then, the whole surface was exposed to ghi rays with an exposure amount of 600 mJ/cm ² using an aligner (PLA-501F, manufactured by Canon Inc.), and the entire surface was exposed to nitrogen using a vacuum gas replacement oven (450PB8-2P-CP, manufactured by YES Corporation). The heat-hardening process was implemented at a specific temperature for 2 hours under the atmosphere, and a cured film was produced. The thickness of the cured film was measured using a level difference meter (P-15, manufactured by KLA-Tenchore). This cured film was cut into a length of 80 mm and a width of 60 mm or a length of 40 mm and a width of 30 mm using a wafer dicing machine (manufactured by DISCO, model name DAD-2H/6T), immersed in a 10% hydrochloric acid aqueous solution and removed from a silicon wafer The film was peeled off to make a film sample.

For the film samples, the specific permittivity and dielectric loss tangent at 10, 28, 40, and 60 GHz were calculated using the resonance perturbation method. The details of the measurement method are as follows. (test methods) Perturbation method split cylindrical resonator method (device configuration) Network analyzer: PNA Network analyzer E5224B (manufactured by Agilent technologies) Split cylinder resonator: CR-710 (manufactured by Kanto Electronics Application Development Co., Ltd., measurement frequency: about 10 GHz), CR-728 (manufactured by Kanto Electronics Application Development Co., Ltd., measurement frequency: about 28 GHz), CR-740 (Kanto Electronics Co., Ltd., measurement frequency: about 28 GHz) Manufactured by Application Development Co., Ltd., measurement frequency: about 40 GHz), CR-760 (manufactured by Kanto Electronics Application Development Co., Ltd., measurement frequency: about 60 GHz)

(3) Measurement of weight loss rate The photosensitive resin composition was spin-coated on a 6-inch silicon wafer so that the film thickness after curing was about 10 μm, and pre-baked at 110° C. for 180 seconds on a hot plate Then, it heated at 230 degreeC for 2 hours under nitrogen atmosphere using a vacuum gas replacement oven (450PB8-2P-CP, the YES company make), and obtained the cured polyimide coating film. The film thickness was measured by a film thickness measuring apparatus, Lambda ACE (manufactured by Dainippon Screen Co., Ltd.). The obtained polyimide coating film was scraped off, and the temperature was raised at 10°C/min from room temperature using a thermogravimetric measuring apparatus (manufactured by Shimadzu Corporation, TGA-50), and the weight of the film at 230°C was set as W ₂₃₀ , Let the weight of the film at 320°C be W ₃₂₀ , and the weight of the film at 350° C to be W ₃₅₀ , respectively, the following formulas were calculated: 320° C. weight reduction rate (%)=(W ₂₃₀ -W ₃₂₀ ) /W ₂₃₀ 350 ℃ weight reduction rate (%) = (W ₂₃₀ -W ₃₅₀ )/W ₂₃₀

[(A) Production of Polyimide Precursor] <Production Example 1> ((A) Synthesis of Polyimide Precursor (Polymer A-1)) Put 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) into a 2-liter separable flask, and add 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and γ-butyrolactone 400 ml of ester, 79.1 g of pyridine was added while stirring at room temperature to obtain a reaction mixture. After the heat generation due to the reaction was completed, it was left to cool to room temperature, and was further left to stand for 16 hours.

Then, under ice-cooling, while stirring, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture for 40 minutes, and then While stirring, a suspension of 175.9 g of 2,2-bis{4-(4-aminophenoxy)phenyl}propane (BAPP) in 350 ml of γ-butyrolactone was added over 60 minutes. . Further, after stirring at room temperature for 2 hours, 30 ml of ethanol was added, followed by stirring for 1 hour, and then 400 ml of γ-butyrolactone was added. The resulting precipitate in the reaction mixture was removed by filtration to obtain a reaction solution.

The obtained reaction solution was added to 3 liters of ethanol to generate a precipitate containing crude polymer. The produced crude polymer was collected by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was purified using an anion exchange resin (“Amberlyst ^™ 15” manufactured by Organo Co., Ltd.) to obtain a polymer solution. The obtained polymer solution was added dropwise to 28 liters of water to precipitate a polymer, and the obtained precipitate was collected by filtration and then vacuum-dried to obtain a powdery polymer A-1. The weight average molecular weight (Mw) of this polymer A-1 was measured and found to be 22,000. The imide group concentration of each repeating unit of the polyimide cured film obtained from the polymer A-1 was 19.4 wt%.

<Production Example 2> ((A) Synthesis of Polyimide Precursor (Polymer A-2)) In the above-mentioned Production Example 1, except that 93.0 g of 4,4'-oxydiphenylamine (ODA) was used in place of 175.9 g of BAPP, the reaction was carried out in the same manner as in the method described in Production Example 1, whereby polymerization was obtained. Object A-2. The weight average molecular weight (Mw) of this polymer A-2 was measured and found to be 22,000. The imide group concentration of each repeating unit of the polyimide cured film obtained from the polymer A-2 was 27.4 wt %.

<Production Example 3> ((A) Synthesis of Polyimide Precursor (Polymer A-3)) In the above production example 1, 260.2 g of 4,4'-(4,4'-isopropylidene diphenoxy) acid dianhydride (BPADA) was used instead of 155.1 g of ODPA, and 2,2'-dimethyl A polymer A was obtained by reacting in the same manner as in the method described in Production Example 1, except that 92.88 g of biphenyl-4,4'-diamine (m-TB) was used in place of 175.9 g of BAPP. -3. The weight average molecular weight (Mw) of this polymer A-3 was measured and found to be 23,000. The imide group concentration of each repeating unit of the polyimide cured film obtained from the polymer A-3 was 19.1 wt%.

<Production Example 4> ((A) Synthesis of Polyimide Precursor (Polymer A-4)) In the above-mentioned Production Example 1, the reaction was carried out in the same manner as the method described in Production Example 1, except that 109.1 g of pyromellitic anhydride was used in place of 155.1 g of ODPA, and 93.0 g of ODA was used in place of 175.9 g of BAPP. , thereby obtaining polymer A-4. The weight average molecular weight (Mw) of this polymer A-4 was measured and found to be 20,000. The imide group concentration of each repeating unit of the polyimide cured film obtained from the polymer A-4 was 33.5 wt%.

[Production of Photosensitive Resin Composition] The following compounds were used in the examples. Photopolymerization initiator B-1: TR-PBG-3057 (manufactured by Changzhou Qiangli Electronics Co., Ltd.) Solvent D-1: γ-Butyrolactone (GBL)

<Example 1> A negative photosensitive resin composition was prepared by the following method using the polyimide precursor A-1. Dissolved in A-1: 100 g as (A) polyimide precursor, B-1: 5 g as (B) photopolymerization initiator, and (D) D-1: 100 g. Furthermore, a small amount of GBL was added to adjust the viscosity of the obtained solution to about 40 poise, thereby preparing a negative photosensitive resin composition. A cured film was produced and evaluated from this composition according to the above-mentioned method. Furthermore, the heat-hardening step (step (5)) was performed at 230° C. for 2 hours with a pressure of 380 torr. The results are shown in Table 1 below.

<Examples 1 to 7, Comparative Examples 1 to 4> It was prepared with the compounding ratio shown in Table 1 below, and the same evaluation as Example 1 was performed using the temperature and pressure of the heat-hardening step shown in Table 1.

<Examples 8, 9> Prepared at the mixing ratio shown in Table 1 below, and performed the same evaluation as Example 1 using the pressure shown in Table 1. In addition, the heat hardening process was performed at 150 degreeC for 1 hour, and it heated up and performed at 230 degreeC for 1 hour after that.

[Table 1] [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 (A) Polyimide precursor (g) A-1 100 100 100 100 100 100 100 A-2 100 100 100 100 A-3 100 A-4 100 (B) Sensitizer (g) B-1 5 5 5 5 5 5 5 5 5 5 5 5 5 (D) Solvent (g) D-1 200 200 200 200 200 200 200 200 200 200 200 200 200 temperature(℃) 230 230 170 170 230 230 230 150/230 150/230 170 230 230 230 Decompression degree (torr) 380 380 380 380 380 200 50 380 380 760 760 760 380 Imide group concentration (%) 19.4 27.4 19.4 27.4 19.1 19.4 19.4 19.4 27.4 19.4 19.4 27.4 33.5 320℃ weight reduction rate (%) 0.40 0.56 2.28 2.69 0.39 0.36 0.36 0.44 0.63 3.42 0.60 0.85 0.69 350℃ weight reduction rate(%) 1.45 2.05 4.97 5.44 1.43 1.31 1.31 1.52 2.15 6.24 1.82 2.57 2.50 Dk(10 GHz) 3.05 3.30 3.07 3.33 2.96 3.05 3.05 3.05 3.30 3.04 3.06 3.3 3.42 Df(10 GHz) 0.0065 0.0086 0.0084 0.0097 0.0049 0.0063 0.0064 0.0069 0.0087 0.0103 0.0080 0.0106 0.0105 Dk(40 GHz) 2.99 3.25 3.02 3.28 2.91 3.04 3.04 3.04 3.25 3.02 3.02 3.26 3.39 Df(40 GHz) 0.0076 0.0089 0.0086 0.0099 0.0057 0.0074 0.0076 0.0079 0.0088 0.0122 0.0103 0.0126 0.0126 (Df ₄₀ - Df ₁₀ )/Df ₁₀ 0.17 0.03 0.02 0.01 0.17 0.18 0.19 0.15 0.01 0.19 0.29 0.20 0.20

According to Table 1, the cured films of Examples can obtain cured films with low frequency dependence of dielectric loss tangent. Moreover, the weight reduction rate at the time of heating a cured film at 320 degreeC and 350 degreeC fell with respect to a comparative example. [Industrial Availability]

According to the manufacturing method of the polyimide cured film of this invention, the frequency dependence of a dielectric loss tangent is low, and the thermogravimetric reduction at the temperature higher than the heat-hardening temperature can be provided. Therefore, the manufacturing method of the polyimide cured film of this invention can be utilized suitably in fields, such as a semiconductor device and a multilayer wiring board, for example.

Claims (16)

A manufacturing method of a polyimide hardened film is characterized in that comprising the following steps: (1) the step of coating a photosensitive resin composition comprising a polyimide precursor on a substrate, and forming a photosensitive resin layer on the substrate; (2) the steps of drying and heating the obtained photosensitive resin layer; (3) the step of exposing the obtained photosensitive resin layer; (4) a step of developing the obtained photosensitive resin layer; and (5) the step of forming a cured film by heat-treating the photosensitive resin layer remaining on the substrate at 150°C to 250°C; The above-mentioned steps (2) and/or (5) are carried out under the pressure of 50 torr or more and 580 torr or less, and in the polyimide of the obtained polyimide cured film, relative to the polyimide containing tetracarboxylic acid The molecular weight of the repeating unit of the structure of the acid and the diamine, the ratio of the imino group occupied, that is, the concentration of the imino group is 12 wt% to 30 wt%. The manufacturing method of the polyimide cured film of claim 1, wherein the dielectric loss tangent of the cured film obtained in step (5) at a frequency of 10 GHz obtained by the perturbation method of split cylindrical resonator is 0.001 ~0.007. The manufacturing method of the polyimide cured film of claim 1 or 2, wherein the above step (5) is carried out under a pressure of 50 torr or more and 580 torr or less. The manufacturing method of the polyimide cured film of claim 3, wherein in the above-mentioned step (5), the temperature change from the set temperature when the set heat curing temperature is reached is 30.0° C. or less. The method for producing a cured polyimide film according to any one of claims 3 to 5, wherein in the region where the temperature change in the above step (5) is 9.5°C/min or less, the pressure change is within 150 torr. The manufacturing method of the polyimide cured film according to any one of claims 1 to 5, wherein the weight reduction rate of the obtained polyimide cured film when heated to 320° C. is 0.01% to 0.5%. The method for producing a cured polyimide film according to any one of claims 1 to 6, wherein the weight reduction rate of the obtained cured polyimide film when heated to 350° C. is 0.1% to 1.5%. The method for producing a cured polyimide film according to any one of claims 1 to 7, wherein the cured polyimide film obtained satisfies the following formula (i): 0.001＜(tanδ40－tanδ10)/tanδ10＜0.2 (i) {where, tanδ40 is the dielectric loss tangent at a frequency of 40 GHz obtained by the perturbation-mode split cylindrical resonator method, and tanδ10 is the dielectric loss at a frequency of 10 GHz obtained by the perturbation-mode split cylindrical resonator method loss tangent}. A polyimide cured film for forming an interlayer insulating film for rewiring, which has a dielectric loss tangent of 0.001 to 0.009 when measured by a perturbation method split cylindrical resonator method at a frequency of 10 GHz, and the polyimide It has the structure represented by the following general formula (10): [Chemical 1]

{In the formula, R ₂₁ and R ₂₂ are each independently a hydrogen atom or a valent organic group having 1 to 6 carbon atoms, and * represents a linker}. The cured polyimide film for forming an interlayer insulating film for rewiring according to claim 9, wherein the polyimide contains at least one of the structures represented by the following formula:

{In the formula, * represents a connecting part}. As claimed in claim 9 or 10, the cured polyimide film for forming an interlayer insulating film for rewiring has a weight reduction rate of 0.01% to 0.5% when heated to 320°C, and a weight reduction rate of 0.01% to 0.5% when heated to 350°C 0.1% to 1.5%. A polyimide cured film for forming an interlayer insulating film for rewiring, which has a weight reduction rate of 0.01% to 0.5% when heated to 320° C., and a weight reduction rate of 0.1% to 1.5% when heated to 350° C. In addition, the dielectric loss tangent when measured at a frequency of 40 GHz by the perturbation-type split cylindrical resonator method is 0.0021 to 0.0085. The method for producing a cured polyimide film according to any one of claims 1 to 8, wherein the polyimide precursor has a structure represented by the following general formula (1):

{In the formula, X ₁ is a tetravalent organic group with 6-40 carbon atoms, Y ₁ is a divalent organic group with 6-40 carbon atoms, n ₁ is an integer of 2-150, and R ₁ and R ₂ are each independently is a hydrogen atom or a monovalent organic group with 1 to 40 carbon atoms; wherein, at least one of R ₁ and R ₂ is a group represented by the following general formula (2):

(in the formula, R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m ₁ is an integer of 2 to 10)}. The method for producing a cured polyimide film according to any one of claims 1 to 8 and 13, wherein the photosensitive resin composition contains a photopolymerization initiator. The method for producing a cured polyimide film according to claim 14, wherein in the general formula (1), X ₁ is at least one of the structures represented by the following formula:

[hua 6]

{In the formula, R6 is a valent group selected from the group consisting of hydrogen atom, fluorine atom, hydrocarbon group of C1-C10, and fluorine-containing hydrocarbon group of C1-C10, l is an integer selected from 0-2, m is is an integer selected from 0-3, and n is an integer selected from 0-4}. The method for producing a cured polyimide film according to any one of claims 13 to 15, wherein in the general formula (1), X ₁ is at least one of the structures represented by the following formula:

{In the formula, * represents a connecting part}.