TW201826024A - Pattern forming method, method for producing laminate and method for producing electronic device - Google Patents

Abstract

Provided are: a pattern forming method which is capable of forming two or more patterns having different thicknesses with high resolution; a method for producing a laminate; and a method for producing an electronic device. A pattern forming method for forming two or more patterns having different thicknesses at the same time by forming a negative photosensitive resin composition layer with use of a negative photosensitive resin composition containing a resin and a photopolymerization initiator and by subjecting the negative photosensitive resin composition layer to light exposure and development. The thickness of the thickest pattern among the patterns having different thicknesses and formed at the same time is from 1.5 to 10 times the thickness of the thinnest pattern; and a negative photosensitive resin composition having a difference of 600 mJ/cm2 or more between the maximum value and the minimum value of light exposure amount, with which a pattern having a thickness of 15 [mu]m and a line width of 15 [mu]m or less is able to be resolved, is used in this pattern forming method.

Description

Pattern forming method, laminated body manufacturing method, and electronic device manufacturing method

The present invention relates to a method for forming a pattern, a method for manufacturing a laminated body, and a method for manufacturing an electronic device.

Since polyimide is excellent in heat resistance and insulation, it is used for an insulating layer or the like of an electronic device. In addition, since polyimide has a low solubility in a solvent, it is applied to a support or the like in a state of a precursor (polyimide precursor) before the cyclization reaction, and then the polyimide precursor is heated. When the material is cyclized to form a cured film.

For example, Patent Documents 1 and 2 describe forming a pattern using a negative photosensitive resin composition containing a polyfluorene imide precursor and a photopolymerization initiator. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-191749 [Patent Document 2]: Japanese Patent Laid-Open No. 2014-201695

In recent years, when a pattern is formed using a negative photosensitive resin composition, a pattern may be formed on a negative photosensitive resin composition formed on a support having a step, or a plurality of negative photosensitive resin compositions are laminated. In addition, two or more patterns are formed. In this case, two or more patterns having different thicknesses are formed. When two or more patterns having different thicknesses are formed, a method is used in which the mask and the exposure amount are changed according to the pattern thickness. However, in this case, a plurality of exposure steps are required, and the number of steps increases. In addition, as the difference in thickness between the patterns becomes larger, there is a tendency that it is difficult to form a desired pattern shape.

In addition, there is no description or suggestion about forming a pattern having a different thickness in Patent Documents 1 and 2.

An object of the present invention is to provide a pattern forming method, a laminated body manufacturing method, and an electronic device manufacturing method capable of forming two or more patterns having different thicknesses with a wide exposure and good resolution.

Based on the above-mentioned problems, the inventors conducted research and found that the above-mentioned problems can be solved by the pattern forming method shown below, and the present invention has been completed. The present invention provides the following. <1> A pattern forming method using a negative photosensitive resin composition containing a resin and a photopolymerization initiator to form a negative photosensitive resin composition layer on a support, and performing a negative photosensitive resin composition layer Exposure and development simultaneously form two or more patterns with different thicknesses. Among the patterns with different thicknesses formed simultaneously, the thickest pattern has a thickness of 1.5 to 10 times the thickness of the thinnest pattern, and is used as a negative photosensitive resin. As the composition, a negative photosensitive resin composition capable of analyzing a maximum exposure value and a minimum exposure value of a pattern having a thickness of 15 μm and a line width of 15 μm or less is 600 mJ / cm ² or more. <2> The pattern forming method according to <1>, in which two or more negative photosensitive resin compositions are laminated on a support, and two or more negative photosensitive resin composition layers are exposed and At the same time, two or more patterns having different thicknesses are formed while being developed. <3> The pattern forming method according to <1> or <2>, wherein the thickness of the thickest pattern among the patterns having different thicknesses formed simultaneously is 1.75 to 8 times the thickness of the thinnest pattern. <4> The pattern forming method according to <1> or <2>, wherein the thickness of the thickest pattern among the patterns having different thicknesses formed at the same time is 2 to 6 times the thickness of the thinnest pattern. <5> The pattern forming method according to any one of <1> to <4>, in which the maximum and minimum exposure amounts of a pattern capable of analyzing a pattern having a thickness of 15 μm and a line width of 15 μm or less are used as the negative photosensitive resin composition. The difference in values is a negative photosensitive resin composition of 900 mJ / cm ² or more. <6> The pattern forming method according to any one of <1> to <5>, a resin-based polyfluorene imide precursor. <7> The pattern forming method according to <6>, the polyimide precursor is represented by the following formula (1), [chemical formula 1] In formula (1), A ²¹ and A ²² each independently represent an oxygen atom or -NH-, R ²¹ represents a divalent organic group, R ²² represents a tetravalent organic group, and R ²³ and R ²⁴ each independently represent a hydrogen atom or Monovalent organic group. <8> The pattern forming method according to <7>, in the formula (1), at least one of R ²³ and R ²⁴ includes a radical polymerizable group. <9> The pattern forming method described in <7> or <8>, wherein R ²² in formula (1) contains a tetravalent group of an aromatic ring. <10> The pattern forming method according to any one of <1> to <9>, further comprising a step of forming a metal layer. <11> A method for producing a laminated body, comprising the pattern forming method according to any one of <1> to <10>. <12> A method for manufacturing an electronic device, comprising the pattern forming method according to any one of <1> to <10>. [Inventive effect]

According to the present invention, it is possible to provide a pattern forming method capable of forming two or more patterns having different thicknesses with a wide exposure and good resolution, a method for manufacturing a laminated body, and a method for manufacturing an electronic device.

The description of the constituent elements in the present invention described below may be made based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment. In the present specification, a group (atomic group) is labeled. The unregistered and unsubstituted labels include both a group having no substituent and a group having a substituent. For example, "alkyl" includes not only an alkyl group (unsubstituted alkyl group) without a substituent, but also an alkyl group (substituted alkyl group) with a substituent. As long as "exposure" is not specifically limited in this specification, in addition to exposure using light, drawing using a particle beam such as an electron beam and an ion beam is also included in the exposure. In addition, as the light used for the exposure, actinic rays such as bright line spectrum of a mercury lamp, excimer laser, extreme ultraviolet (EUV light), X-rays, and electron beams, or radiation are generally mentioned. In the present specification, a numerical range indicated by "~" means a range including numerical values described before and after "~" as a lower limit value and an upper limit value. In this specification, "(meth) acrylate" means either or both of "acrylate" and "methacrylate", and "(meth) allyl" means "allyl" and "formyl" "(Meth) acrylic" means either or both of "acrylic" and "methacrylic", and "(meth) acryl" refers to "acryl" Or "methacryl". In this specification, the term "step" is not only an independent step, but even if it cannot be clearly distinguished from other steps, if the intended effect of the step can be achieved, it is also included in this term. In the present specification, the solid content concentration refers to the mass percentage of components other than the solvent with respect to the total mass of the composition. In addition, unless otherwise stated, the solid content concentration means the concentration at 25 ° C. In this specification, unless otherwise stated, weight average molecular weight (Mw) and number average molecular weight (Mn) are measured based on gel permeation chromatography (GPC), and are defined as polystyrene conversion values. In this specification, for example, HLC-8220 (manufactured by TOSOH CORPORATION) can be used as the weight average molecular weight (Mw) and the number average molecular weight (Mn), and the protective column HZ-L, TSKgel Super HZM-M, and TSKgel Super can be used as the column. HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). Unless otherwise stated, the eluent was measured by THF (tetrahydrofuran). In addition, unless otherwise stated, the detection was performed using a wavelength 254 nm detector using UV rays (ultraviolet rays).

<Pattern formation method> The pattern formation method of the present invention uses a negative photosensitive resin composition containing a resin and a photopolymerization initiator to form a negative photosensitive resin composition layer, and performs the negative photosensitive resin composition layer. Exposure and development to form two or more patterns with different thicknesses at the same time. The thickness of the thickest pattern among the patterns with different thicknesses formed at the same time is 1.5 to 10 times the thickness of the thinnest pattern. As the object, a negative photosensitive resin composition having a thickness of 15 μm and a line width of 15 μm or less and a maximum and minimum exposure amount capable of analyzing a pattern is 600 mJ / cm ² or more.

According to the present invention, a negative photosensitive resin composition having a difference between the maximum value and the minimum value of the exposure amount of 600 mJ / cm ² or more is used as the negative photosensitive resin composition, so that a wide exposure amount can be used simultaneously and at a good quality. A resolution of 2 or more forms two or more patterns with different thicknesses. Therefore, patterns with different thicknesses can be formed with a small number of steps and good resolution. Moreover, since the above-mentioned pattern can be formed with a wide exposure amount, even if the performance of the photosensitive composition changes (e.g., lower sensitivity) with time, the device is deformed, etc., the effect of obtaining a desired pattern can be expected . In addition, in the present invention, the simultaneous formation of two or more patterns with different thicknesses means that two or more patterns with different thicknesses are formed by one exposure and development operation.

In the present invention, the maximum and minimum values of the exposure amount capable of analyzing a pattern having a thickness of 15 μm and a line width of 15 μm or less are values defined below. In pattern analysis, if the amount of exposure during exposure is too low, the hardening of the negative photosensitive resin composition layer does not proceed sufficiently, and a desired pattern cannot be analyzed. In addition, if the exposure amount is too high, curing of the unexposed portion of the mask edge portion cannot be performed sufficiently, and a pattern becomes thick, and a pattern of a desired size cannot be analyzed. The negative photosensitive resin composition was applied to a support and dried to form a negative photosensitive resin composition layer having a thickness of 15 μm, and the exposure amount was changed to expose and develop the negative photosensitive resin composition layer having a thickness of 15 μm. When the unexposed portion is removed to form a pattern with a thickness of 15 μm and a line width of 15 μm or less (preferably 15 μm), changing the exposure amount during exposure to perform exposure can analyze a thickness of 15 μm and a line width of 15 μm or less (preferably The value of the lowest exposure amount among the exposure amounts of a pattern having a line width of 15 μm) is defined as the minimum exposure amount, and the highest exposure value is set to the maximum exposure amount. For example, the above pattern can be analyzed at an exposure amount up to 100 mJ / cm ² , but if it is less than 100 mJ / cm ² , the curing cannot be sufficiently performed and the above pattern cannot be analyzed, and the minimum exposure amount is 100 mJ / cm ² . Furthermore, for example, at 1000mJ / ² cm until the exposure amount of each can be the pattern, but if greater than 1000mJ / cm ^2, the pattern thickening occurs when the pattern can not be resolved, 1000mJ / cm ² exposure amount of the maximum value. As the light (radiation) used in the exposure, radiation such as visible rays, ultraviolet rays, extreme ultraviolet rays, charged particle beams, and X-rays can be appropriately selected and used, but light (radiation) having a wavelength in a range of 190 to 450 nm is preferable. For example, it is preferable to perform pattern exposure using an exposure device such as a stepper through a mask having a square Bayer pattern per 1 μm from 1 μm to 15 μm. As the light (radiation) that can be used during exposure, ultraviolet rays such as g-rays and i-rays are preferred, and i-rays are more preferred. In the present invention, the line width of the pattern refers to the line width of the development removal portion (negative pattern) of the negative photosensitive resin composition layer. In the present invention, when the exposed width of the substrate is 0.8 to 1.2 times the mask size, a pattern of a desired size is analyzed. For example, when a pattern is formed using a mask having a line width of 15 μm, a pattern with a line width of 15 μm is analyzed when the exposed width of the substrate is 15 ± 3 μm.

In the negative photosensitive resin composition used in the pattern forming method of the present invention, the difference between the maximum value and the minimum value of the exposure amount is 600 mJ / cm ² or more, preferably 700 mJ / cm ² or more, and 800 mJ / cm ² The above is more preferable, and more than 900mJ / cm ² is more preferable. The upper limit is not particularly limited. For reasons of shortening the time required in each step, 1800 mJ / cm ² or lower is more preferred, 1700 mJ / cm ² or lower is more preferred, and 1600 mJ / cm ² or lower is further preferred. The negative photosensitive resin composition is in a range of 50 to 500 mJ / cm ² (more preferably, at least one selected from the maximum value and the minimum value of the exposure amount (preferably, the minimum value of the exposure amount)). It is preferably in the range of 100 to 400 mJ / cm ² ). Both the maximum value and the minimum value of the exposure amount are particularly preferably in a range of 10 to 2000 mJ / cm ² (more preferably in a range of 50 to 1800 mJ / cm ² ).

As a method of adjusting the difference between the maximum value and the minimum value of the exposure amount in the negative photosensitive resin composition to 600 mJ / cm ² , a method of adjusting the ratio of the resin to the photopolymerization initiator may be mentioned. When the resin and the radical polymerizable compound are used together, it is also preferable to adjust the ratio of the resin, the radical polymerizable compound, and the photopolymerization initiator. For example, the ratio (mass ratio) of the resin to the radical polymerization initiator is adjusted to a range of 5: 1 to 10: 1, and the ratio (mass ratio) of the radical polymerization initiator to the photopolymerization initiator is adjusted. It is also preferable to adjust the range from 2: 1 to 8: 1.

In the present invention, the thickness of the thickest pattern and the thickness of the thinnest pattern among the patterns having different thicknesses formed at the same time refer to the thickness of the pattern formed by negative development. For example, A1, B1, and C1 in FIG. 1 are the thicknesses of the patterns, B1 in FIG. 1 corresponds to the thickness of the thickest pattern, and A1 in FIG. 1 corresponds to the thickness of the thinnest pattern. Reference numeral 10 in FIG. 1 denotes a resin layer formed using a negative photosensitive resin composition, and reference numeral 20 denotes a structure such as a support or a metal layer. The pattern shown in FIG. 1 can be formed as follows. That is, a negative photosensitive resin composition layer 11 is formed on a support 20 having steps such as unevenness (FIG. 2 (A)), and then performed through a mask 50 having a pattern. After exposure (FIG. 2 (B)), the unexposed part is removed by development (FIG. 2 (C)), and a desired pattern can be formed.

In the present invention, the thickness of the thickest pattern among the patterns having different thicknesses formed at the same time is 1.5 to 10 times the thickness of the thinnest pattern, preferably 1.75 to 8 times, and more preferably 2 to 6 times. In the present invention, the thickness of the pattern means the thickness of the pattern after curing.

The thickness of the pattern formed by the pattern forming method of the present invention is preferably 0.05 to 100 μm. The upper limit is preferably 90 μm or less, more preferably 75 μm or less, and even more preferably 50 μm or less. The lower limit is preferably 0.1 μm or more, more preferably 1 μm or more, and more preferably 5 μm or more. In the present invention, the thickness of the thickest pattern among the patterns having different thicknesses formed simultaneously is preferably 0.1 to 100 μm. The upper limit is preferably 90 μm or less, more preferably 75 μm or less, and even more preferably 50 μm or less. The lower limit is preferably 0.5 μm or more, more preferably 1 μm or more, and more preferably 5 μm or more. In the present invention, the thickness of the thinnest pattern among the patterns having different thicknesses formed at the same time is preferably 0.05 to 75 μm. The upper limit is preferably 50 μm or less, and more preferably 30 μm or less. The lower limit is preferably 0.1 μm or more, more preferably 1 μm or more, and more preferably 3 μm or more.

In the pattern forming method of the present invention, the above-mentioned negative photosensitive resin composition is laminated on the support body by two or more layers, and the negative photosensitive resin composition layer formed by laminating more than two layers is simultaneously exposed and developed to form simultaneously. Two or more patterns having different thicknesses are preferred. When two or more negative-type photosensitive resin compositions are laminated, the thickness of the negative-type photosensitive resin composition layer may sometimes vary due to the unevenness of the support serving as a base. Therefore, a pattern with a larger thickness difference is sometimes formed, but according to the present invention, even in this case, two or more patterns with different thicknesses can be formed simultaneously and with good resolution.

Hereinafter, the pattern forming method of the present invention will be specifically described.

The method for producing a pattern of the present invention includes a step of forming a negative photosensitive resin composition layer on a support using a negative photosensitive resin composition containing a resin and a photopolymerization initiator (negative photosensitive resin composition layer Formation step). In the present invention, as the negative-type photosensitive resin composition, a negative-type photosensitive resin composition having a difference between the maximum value and the minimum value of the exposure amount of 600 mJ / cm ² or more is used. Details of the negative-type photosensitive resin composition will be described later.

The type of the support can be appropriately determined depending on the application. Examples include inorganic substrates, resin substrates, and resin composite substrates. Examples of the inorganic substrate include a glass substrate, a quartz substrate, a silicon substrate, a silicon nitride substrate, and a composite substrate obtained by vapor-depositing molybdenum, titanium, aluminum, copper, or the like on these substrates. Examples of the resin substrate include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, and poly Carbonate, polyfluorene, polyetherfluorene, polyarylate, allyl diethylene glycol carbonate, polyfluorene, polyfluorene, polyfluorene, imine, polyether, imine, polyindole, Polyphenylene sulfide, polycycloolefin, norbornene resin, fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionic polymer resin, cyanate resin, cross-linking Substrates of synthetic resins such as fumarate diesters, cyclic polyolefins, aromatic ethers, maleimides, olefins, cellulose, and episulfide compounds. These substrates are rarely used directly in the aforementioned form, and generally, depending on the form of the final product, for example, a multilayer structure such as a thin film transistor (TFT) element is formed. When a negative photosensitive resin composition layer is formed on the surface of a negative photosensitive resin composition layer having a metal layer or the like, the metal layer or the negative photosensitive resin composition layer becomes a support.

As a method for applying a negative photosensitive resin composition to a support, coating is preferred. Specific application methods include dip coating method, air knife coating method, curtain coating method, wire rod coating method, gravure coating method, extrusion coating method, spin coating method, and slit scanning. Method, inkjet method, etc. From the viewpoint of the uniformity of the thickness of the negative photosensitive resin composition layer, a spin coating method is more preferred. In the case of the spin coating method, it can be applied at a rotation speed of 500 to 5000 rpm for about 10 seconds to 1 minute. The thickness of the negative photosensitive resin composition layer is preferably applied so that the film thickness after heating becomes 0.05 to 100 μm, and more preferably applied so that it becomes 1 to 50 μm. The thickness of the negative photosensitive resin composition layer to be formed is not necessarily uniform. For example, as shown in FIG. 1, when a negative photosensitive resin composition layer is formed on a surface having irregularities, it may become a negative photosensitive resin composition layer having a different thickness.

In the negative photosensitive resin composition layer forming step, the negative photosensitive resin composition layer formed on the support may be dried. The drying temperature is preferably 50 to 150 ° C, more preferably 70 to 130 ° C, and even more preferably 90 to 110 ° C. The drying time is preferably 30 seconds to 20 minutes, more preferably 1 to 10 minutes, and more preferably 3 to 7 minutes.

The pattern forming method of the present invention includes a step of forming a pattern by exposing and developing a negative photosensitive resin composition layer. Specifically, an exposure step of pattern-wise exposing the negative photosensitive resin composition layer and a development step of forming a pattern by removing unexposed portions of the exposed resin composition layer by development. Further, in the present invention, two or more patterns having different thicknesses are formed simultaneously by exposing and developing the negative photosensitive resin composition layer. When two or more patterns having different thicknesses are formed simultaneously, a negative photosensitive resin composition layer may be formed on a support having unevenness such as unevenness, and the negative photosensitive resin composition layers having different thicknesses may be exposed and developed simultaneously. To form a pattern. Examples of the support having a step such as unevenness include a support in which a structure such as a metal layer is formed on the surface.

In the exposure step, the exposure to the negative photosensitive resin composition layer is preferably performed at a wavelength of 365 nm exposure energy converted into 50 to 10,000 mJ / cm ^2, and more preferably 100 to 8000 mJ / cm ² . The exposure wavelength can be appropriately set in a range of 190 to 1000 nm, and 240 to 550 nm is preferable.

In the developing step, the development of the negative photosensitive resin composition layer is preferably performed using a developing solution. It can be used arbitrarily as a developing solution. A solvent is preferred. The developer can be used without particular limitation. A solvent is preferred. Examples of the solvent used in the developer include organic solvents such as esters, ethers, ketones, aromatic hydrocarbons, and fluorenes. About these details, the solvent demonstrated in the column of the resin composition mentioned later is mentioned. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methyl Methyl oxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfene, ethyl carbitol acetate, butyl carbitol acetate, Propylene glycol methyl ether and propylene glycol methyl ether acetate are more preferred, and cyclopentanone and γ-butyrolactone are more preferred.

The development time is preferably 10 seconds to 5 minutes. The temperature during development is not particularly limited, and it can be performed at 20 to 40 ° C. After the treatment using the developing solution, processing can be further performed. It is preferable to use a solvent different from the developer when developing. For example, it is possible to rinse using a solvent contained in the resin composition. The rinse time is preferably 5 seconds to 1 minute.

It is preferable that the pattern forming method of the present invention includes a heating step of heating the pattern obtained by the developing step. In the heating step, a cyclization reaction of the polyfluorene imide precursor is performed. When the negative photosensitive resin composition contains a radical polymerizable component such as a radical polymerizable compound, curing of the unreacted radical polymerizable component is also performed. Thereby, a pattern excellent in heat resistance and the like can be formed.

As the maximum heating temperature (highest temperature during heating) in the heating step, 100 to 500 ° C is preferable, 140 to 400 ° C is more preferable, and 160 to 350 ° C is more preferable. Heating is preferably performed at a heating rate of 1 to 12 ° C./minute from a temperature of 20 to 150 ° C. to a maximum heating temperature, more preferably 2 to 10 ° C./minute, and still more preferably 3 to 10 ° C./minute. By setting the temperature increase rate to 1 ° C / min or more, it is possible to prevent high volatilization of the amine while ensuring high productivity, and to set the temperature increase rate to 12 ° C / min or less to reduce the residual stress of the obtained film. The temperature at the start of heating is preferably 20 to 150 ° C, more preferably 20 to 130 ° C, and even more preferably 25 to 120 ° C. The temperature at the start of heating refers to the temperature at which heating is started up to the maximum heating temperature. For example, when the negative photosensitive resin composition is applied to a support and dried, the temperature after drying is the heating start temperature. In the heating step, for example, it is preferable to gradually raise the temperature from a temperature 30 to 200 ° C. lower than the boiling point of the solvent contained in the negative photosensitive resin composition. In the heating step, after reaching the maximum heating temperature, heating for 10 to 360 minutes is preferred, heating for 20 to 300 minutes is further preferred, and heating for 30 to 240 minutes is particularly preferred.

The heating in the heating step may be performed in stages. As an example, the temperature can be raised from 25 ° C to 180 ° C at 3 ° C / min, and allowed to stand at 180 ° C for 60 minutes, raised from 180 ° C to 200 ° C at 2 ° C / minute, and left at 200 ° C for 120 minutes. And so on.

The heating step is preferably performed in a low oxygen concentration environment by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the polyfluorene imide precursor or the like. The oxygen concentration is preferably 50 vol ppm or less, and more preferably 20 vol ppm or less.

It is preferable to cool after the heating step. The cooling rate is preferably 1 to 5 ° C / minute.

The pattern forming method of the present invention may include a step of forming a metal layer (metal layer forming step). The metal layer is not particularly limited, and an existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are preferred, and copper is more preferred. The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in Japanese Patent Application Laid-Open No. 2007-157879, Japanese Patent Application No. 2001-521288, Japanese Patent Application Laid-Open No. 2004-214501, and Japanese Patent Application Laid-Open No. 2004-101850 can be used. Examples thereof include photolithography, peeling, electroplating, electroless plating, etching, printing, and a method of combining them. Specifically, a patterning method using a combination of sputtering, photolithography, and etching, and a patterning method using a combination of photolithography and electrolytic plating can be cited. As the thickness of the metal layer, the thickest part is preferably 0.1 to 50 μm, and more preferably 1 to 10 μm.

When the pattern forming method of the present invention includes the step of forming a metal layer, it may further include a step (surface activation treatment step) of performing surface activation treatment on at least a part of the metal layer and the negative photosensitive resin composition layer. The surface activation treatment may be performed only on at least a part of the metal layer, or may be performed only on at least a part of the negative photosensitive resin composition layer after the above development step (after the heating step is performed). You may perform it on at least one part of both a metal layer and a negative photosensitive resin composition layer. The surface activation treatment is usually performed after the metal layer is formed, and the negative-type photosensitive resin composition layer after the development step (and further, the heating step after the heating step) may be subjected to surface activation treatment to form a metal layer. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform surface activation treatment on a part or the whole of a region in the metal layer where a negative photosensitive resin composition layer is formed. In this way, by subjecting the surface of the metal layer to surface activation treatment, it is possible to improve the adhesion to the negative photosensitive resin composition layer provided on the surface. The surface activation treatment is preferably performed on part or all of the negative photosensitive resin composition layer. In this way, by subjecting the surface of the negative photosensitive resin composition layer to surface activation treatment, the adhesion with the metal layer or the negative photosensitive resin composition layer provided on the surface subjected to the surface activation treatment can be improved. The surface activation treatment is selected from plasma treatment, corona discharge treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), based on CF ₄ / O ₂ , Etching treatment of NF ₃ / O ₂ , SF ₆ , NF ₃ , NF ₃ / O ₂ , surface treatment based on ultraviolet (UV) ozone method, immersion in an aqueous hydrochloric acid solution to remove the oxide film, and the inclusion of amine groups and thiols It is preferred that the organic surface treatment agent of at least one of the compounds be impregnated with an organic surface treatment agent, mechanical roughening treatment using a brush, and plasma treatment, especially oxygen plasma treatment using oxygen as a raw material gas. When performing the corona discharge treatment, the energy system is preferably 500 to 200,000 J / m ² , more preferably 1,000 to 100,000 J / m ² , and most preferably 10,000 to 50,000 J / m ² .

After the pattern forming method of the present invention forms the metal layer, it is preferable to perform the negative photosensitive resin composition layer forming step, the exposure step, the developing step, and the heating step in this order again. In addition, it is also preferable to further perform the above-mentioned metal layer forming step after the heating step. Thereby, a resin layer and a metal layer can be laminated | stacked alternately, and a laminated body can be formed.

<Negative-type photosensitive resin composition (resin composition)> Next, the negative-type photosensitive resin composition used for the pattern formation method of this invention is demonstrated. Hereinafter, the negative photosensitive resin composition is also referred to as a resin composition. The negative-type photosensitive resin composition used in the pattern forming method of the present invention includes a resin and a photopolymerization initiator. In the negative photosensitive resin composition in the present invention, it is preferable that the resin contains a radical polymerizable group or a radical polymerizable compound other than the resin. Hereinafter, each component of a negative photosensitive resin composition is demonstrated in detail.

<<Resin> The resin composition in the present invention contains a resin. Examples of the resin include a polyimide precursor, a polybenzoxazole precursor, a polyimide, a polybenzoxazole, an epoxy resin, and a phenol resin. In the present invention, a resin-based polyfluorene imide precursor is preferred. As the polyimide precursor, a polyimide precursor containing a repeating unit represented by the formula (1) is preferable. Formula (1) [Chemical Formula 2] In formula (1), A ²¹ and A ²² each independently represent an oxygen atom or -NH-, R ²¹ represents a divalent organic group, R ²² represents a tetravalent organic group, and R ²³ and R ²⁴ each independently represent a hydrogen atom or Monovalent organic group.

A ²¹ and A ²² each independently represent an oxygen atom or -NH-, and an oxygen atom is preferred.

R ²¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and an aryl group, a linear or branched aliphatic group having 2 to 20 carbon atoms, and a cyclic group having 6 to 20 carbon atoms. An aliphatic group, an aryl group having 6 to 20 carbons, or a group including a combination thereof is preferable, and a group including an aryl group having 6 to 20 carbons is more preferable. Examples of the aryl group include the following.

[Chemical Formula 3] In the formula, A is a single bond or a hydrocarbon group having 1 to 10 carbon atoms, -O-, -C (= O)-, -S-, -S (= O) _2- , and-which may be substituted with a fluorine atom. NHCO- and the groups in these combinations are preferred, single bond, selected from alkylene groups having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -C (= O)-, -S The group in-, -SO ₂ -is more preferably selected from -CH _2- , -O-, -S-, -SO _2- , -C (CF ₃ ) _2- , -C (CH ₃ ) ₂ -A divalent radical of-is more preferable.

Specific examples of R ²¹ include diamine residues remaining after removal of the amine group of the following diamines. Selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diamine Cyclohexane, 1,2-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane or 1,4-bis (aminomethyl) cyclohexane, Bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophorone di Amine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether And 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Hydrazone and 3,3'-diaminodiphenylphosphonium, 4,4'-diaminodiphenylsulfide and 3,3'-diaminodiphenylsulfide, 4,4'-diaminediphenyl Benzophenone and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4 ' -Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2- Bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxy Phenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) fluorene, bis (4-amino-3-hydroxyphenyl) fluorene, 4,4'-diaminopara-terphenyl, 4 , 4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl ] 碸, bis [4- (2-aminophenoxy) phenyl] fluorene, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) Anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylphosphonium, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-amino Phenoxy) benzene, 1,3-bis (4-aminophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl -4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-amino ) -10-hydroanthracene, 3,3 ', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone , 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4,4'- Dimethyl-3,3'-diaminodiphenylphosphonium, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diamine Cumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2 , 4,6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisilaxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1 2,2-bis (4-aminophenyl) ethane, diaminobenzidine aniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3 -Bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradefluorofluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4 -(2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] Fluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, p-bis (4-amino-2-tri Fluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoro Methylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylphosphonium, 4,4'-bis (3-amino-5- Trifluoromethylphenoxy) diphenylphosphonium, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3 ', 5 , 5'-tetramethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diamino-2 Of 2,2'-bis (trifluoromethyl) biphenyl, 2,2 ', 5,5', 6,6'-hexafluorobenzidine and 4,4 '''-diamine tetraphenyl At least one diamine.

In addition, as examples of R ²¹ , diamine residues remaining after removal of the amine group of the diamines (DA-1) to (DA-18) shown below can be mentioned.

[Chemical Formula 4]

[Chemical Formula 5]

In addition, as an example of R ²¹ , a diamine residue remaining after removal of an amine group of a diamine having two or more alkylene glycol units in the main chain may be mentioned. It is preferable to combine a diamine residue containing one or more of two or more ethylene glycol chains and propylene glycol chains in one molecule, and more preferably a diamine residue containing no aromatic ring. Examples include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 ( The above are trade names, manufactured by HUNTSMAN Corporation), 1- (2- (2- (2-aminopropyloxy) ethoxy) propoxy) propane-2-amine, 1- (1- (1- ( 2-Aminopropoxy) propane-2-yl) oxy) propane-2-amine and the like are not limited thereto. The structures of JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, and EDR-176 are shown below.

[Chemical Formula 6]

In the above, x, y, and z are average values.

In formula (1), R ²² represents a tetravalent organic group, a tetravalent group containing an aromatic ring is more preferred, and a group represented by the following formula (1-1) or formula (1-2) is more preferred.

Formula (1-1) [Chemical Formula 7] In the formula (1-1), R ¹¹² is a single bond or a hydrocarbon group having 1 to 10 carbon atoms, -O-, -CO-, -S-, -SO _2- , and -NHCO-, which may be substituted with a fluorine atom. And a group in a combination thereof is preferred, and a single bond or a group selected from the group consisting of an alkylene group having 1 to 3 carbon atoms, -O-, -CO-, -S-, and -SO ₂ -which may be substituted by a fluorine atom. The divalent group is more preferably selected from the group consisting of -CH _2- , -C (CF ₃ ) _2- , -C (CH ₃ ) _2- , -O-, -CO-, -S-, and -SO _The divalent group in the 2- group is further preferred.

Formula (1-2) [Chemical Formula 8]

Examples of R ²² include tetracarboxylic acid residues remaining after the acid anhydride group is removed from the tetracarboxylic dianhydride. Specific examples thereof include tetracarboxylic acid residues remaining after removing acid anhydride groups from the following tetracarboxylic dianhydrides. Selected from pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'- Diphenylmethanetetracarboxylic dianhydride, 2,2 ', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2, 3,3 ', 4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxo diphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1, 4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride , 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4 , 5,6-naphthalenetetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-fluorenetetracarboxylic dianhydride, 1,2, 4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis (2,3 -Dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride and their carbon number 1 to 6 alkyl derivatives and Alkoxy derivative having 1 to 6 of at least one tetracarboxylic dianhydride.

Examples of R ²² include tetracarboxylic acid residues remaining after removing acid anhydride groups from the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below. [Chemical Formula 9]

From the viewpoint of the solubility with respect to the alkaline developer, it is preferable that R ²² has an OH group. More specifically, examples of R ²² include tetracarboxylic acid residues remaining after removing acid anhydride groups from the above (DAA-1) to (DAA-5).

In formula (1), R ²³ and R ²⁴ each independently represent a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group represented by R ²³ and R ²⁴ include a group including a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, and a radical polymerizable group. In the present invention, at least one of R ²³ and R ²⁴ preferably contains a radical polymerizable group. According to this aspect, the effect of the present invention tends to be more significantly obtained. Moreover, the photosensitive resin composition containing this polyfluorene imide precursor can be used suitably as a negative photosensitive resin composition. Examples of the radical polymerizable group include a group having an ethylenically unsaturated bond. Specific examples of the radical polymerizable group include a vinyl group, a (meth) allyl group, and a group represented by the following formula (III).

[Chemical Formula 10]

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferred. In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH (OH) CH _2- , or a polyoxyalkylene group having 4 to 30 carbon atoms. Preferred examples of R ²⁰¹ include ethylidene, propylidene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, and hexamethylene. methylene, octamethylene, _{dodecamethylene, -CH 2 CH (OH) CH} 2 - , ethyl stretching, stretch propylene, _{trimethylene, -CH 2 CH (OH) CH} 2 - is more good. The combination of R ²⁰⁰ is methyl, and R ²⁰¹ is ethylene.

The carbon number of the linear or branched alkyl group is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, Isopropyl, isobutyl, second butyl, third butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, norbornyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, and fluorene. Group, dicyclohexyl and pinenyl. Among them, cyclohexyl is preferred from the viewpoint of achieving high sensitivity. Examples of the aromatic group include a substituted or unsubstituted benzene ring group, a naphthalene ring group, a pentalene ring group, an indenyl ring group, a fluorene ring group, a heptene ring group, an indenene ring group, and a fluorene ring group. , Fused pentaphenyl ring group, pinene ring group, phenanthrene ring group, anthracene ring group, fused tetraphenyl ring group, fluorene ring group, triphenylene ring group, fluorene ring group, biphenyl ring group, pyrrole ring group, furan Cyclic group, thienyl group, imidazole group, oxazole group, thiazole group, pyridine group, pyrazine group, pyrimidine group, pyridazine group, indazine group, indole group, benzene Benzofuran ring, benzothiophene ring, isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring , Isoquinoline ring, carbazole ring group, morphinyl ring group, acridine ring group, morpholine ring group, thiathracycline group, chromene ring group, xanthene ring group, phenoxaline group, morphine Azine ring group or phenazine ring group. A phenyl ring group is preferred.

In formula (1), when A ²² is an oxygen atom and R ²³ is a hydrogen atom and / or A ²¹ is an oxygen atom and R ²⁴ is a hydrogen atom, the polyfluorene imide precursor may be bonded to a polymer having an ethylenically unsaturated bond. Tertiary amine compounds form conjugate bases. Examples of the tertiary amine compound having such an ethylenically unsaturated bond include N, N-dimethylaminopropylmethacrylate.

In addition, when the alkali is developed, it is preferable that the polyfluorene imide precursor has a fluorine atom in the structural unit from the viewpoint of improving the resolution. The fluorine atom can impart water repellency to the surface of the film at the time of alkali development, and can suppress infiltration from the surface. The fluorine atom content in the polyfluorene imide precursor is preferably 10% by mass or more, and from the viewpoint of solubility in an alkaline aqueous solution, 20% by mass or less is preferable.

In addition, for the purpose of improving the adhesion to the substrate, the polyimide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisilazane, bis (p-aminophenyl) octamethylpentasiloxane, and the like.

In order to improve the storage stability of the resin composition, it is preferable to seal the end of the main chain of the polyfluorene imide precursor with a blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monofluorinated chloride compound, or a monoactive ester compound. Among these, it is more preferable to use a monoamine. Preferred compounds of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7-amine group. Naphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-amine Naphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-amine Naphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid , 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6- Dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, and the like. Two or more of these may be used, or a plurality of different terminal groups may be introduced by reacting a plurality of end-capping agents.

The polyfluorene imide precursor may be composed of a repeating unit represented by formula (1) and other repeating units as other polyfluorine imide precursors. When other repeating units are included, the proportion of other repeating units in the polyimide precursor is preferably 1 to 60 mole%, and more preferably 5 to 50 mole%.

The polyimide precursor in the present invention can be configured so as not to substantially contain other polyimide precursors other than the polyimide precursor containing a repeating unit represented by formula (1). The term “substantially free” means that, for example, the content of the other polyimide precursor contained in the resin composition is 3% by mass or less of the content of the polyimide precursor.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 20,000 to 28,000, more preferably 22,000 to 27,000, and even more preferably 23,000 to 25,000. The dispersion degree (Mw / Mn) of the polyfluorene imide precursor is not particularly determined, but 1.0 or more is preferable, 2.5 or more is more preferable, and 2.8 or more is more preferable. The upper limit of the dispersion degree of the polyimide precursor is not particularly limited, and is preferably 4.5 or less, for example, and can be set to 3.4 or less.

The content of the resin in the resin composition is preferably 20 to 100% by mass, more preferably 50 to 99% by mass, more preferably 60 to 99% by mass, and 70 to 99% by mass relative to the total solid content of the resin composition. % Is particularly good. The content of the polyimide precursor in the resin composition is preferably 20 to 100% by mass, more preferably 50 to 99% by mass, and still more preferably 60 to 99% by mass relative to the total solid content of the resin composition. 70 to 99% by mass is particularly preferred. Moreover, in this invention, you may make it a resin which does not contain substantially other than a polyimide precursor. The term "substantially not included" means, for example, that the content of the resin other than the polyimide precursor contained in the resin composition is 3% by mass or less of the content of the polyimide precursor.

<<< Radical Polymerizable Compound> The resin composition in the present invention may further contain a radical polymerizable compound. By containing a radical polymerizable compound, it can be used suitably as a negative photosensitive resin composition. Furthermore, a cured film having more excellent heat resistance can be formed. As the radical polymerizable compound, a compound having an ethylenically unsaturated bond is preferred, and a compound containing two or more groups having an ethylenically unsaturated bond is more preferred. The radical polymerizable compound may be, for example, any of chemical forms such as a monomer, a prepolymer, an oligomer, a mixture thereof, and a multimer thereof. As the group having an ethylenically unsaturated bond, styryl, vinyl, (meth) acrylfluorenyl, and (meth) allyl are preferred, and (meth) acrylfluorenyl is more preferred. The radical polymerizable compound in the present invention is a component different from the resin.

In the present invention, a monomer-type radical polymerizable compound (hereinafter, also referred to as a radical polymerizable monomer) is a compound different from a polymer compound. The radical polymerizable monomer is typically a low-molecular compound, and a low-molecular compound having a molecular weight of 2,000 or less is preferred, a low-molecular compound having a molecular weight of 1500 or less is more preferred, and a low-molecular compound having a molecular weight of 900 or less is more preferred. The molecular weight of the radical polymerizable monomer is usually 100 or more. The oligomer-type radically polymerizable compound is typically a polymer having a relatively low molecular weight, and a polymer obtained by bonding 10 to 100 radically polymerizable monomers is preferred. As the molecular weight, a polystyrene-equivalent weight average molecular weight by a gel permeation chromatography (GPC) method is preferably 2,000 to 20,000, more preferably 2,000 to 15,000, and even more preferably 2,000 to 10,000.

The number of functional groups of the radically polymerizable compound in the present invention refers to the number of radically polymerizable groups in one molecule. From the viewpoint of resolvability, it is preferable that the resin composition contains at least one type of a bifunctional or more radically polymerizable compound containing two or more radical polymerizable groups, and contains at least one type of a 2- to 4-functional radically polymerizable compound. Better.

Examples of the radical polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amines, and more preferably Esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amines of unsaturated carboxylic acids and polyamine compounds. In addition, it is also preferable to use an addition reaction product of an unsaturated carboxylic acid ester or amidoamine having an affinity substituent such as a hydroxyl group, an amine group, or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and Dehydration condensation reactants of functional or polyfunctional carboxylic acids and the like. In addition, unsaturated carboxylic acid esters or amidoamines having an electrophilic substituent such as an isocyanate group or an epoxy group, and an addition reaction product of a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group or toluene Substituted reactants of unsaturated carboxylic acid esters or amidoamines having detachable substituents such as sulfonyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. As another example, instead of the unsaturated carboxylic acid, a compound group substituted with a vinyl benzene derivative such as unsaturated phosphonic acid, styrene, vinyl ether, allyl ether, or the like can be used. As a specific example, the descriptions in paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-027357 can be referred to, and these contents are incorporated into this specification.

As the radical polymerizable compound, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, and neoopentyl glycol di (meth) acrylate. acrylate), pentaerythritol tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, adipate Alcohols (meth) acrylates, trimethylolpropane tris (acryloxypropyl) ether, tris (acryloxyethyl) isocyanurate, glycerol or trimethylolethane, etc. A compound obtained by adding (meth) acrylate to functional alcohol by adding ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50-6034, Japanese Patent Publication No. 51-37193 (Meth) acrylic acid urethanes described in Japanese Patent Publication No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490 Acrylate as epoxy tree Epoxy acrylates and (meth) acrylic acid reaction product of polyfunctional acrylate or methacrylate, and a mixture of these. The compounds described in paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970 are also preferred.

As the radical polymerizable compound, it is also possible to use a fluorene ring described in Japanese Patent Application Laid-Open No. 2010-160418, Japanese Patent Application Laid-Open No. 2010-129825, Japanese Patent No. 4364216, and the like. Compounds of ethylenically unsaturated groups or cardo resins. Furthermore, as another example, Japanese Unexamined Patent Publication No. 46-43946, Japanese Unexamined Patent Publication No. 1-40337, Japanese Unexamined Patent Publication No. 1-40336, and specific unsaturated compounds described in Japanese Unexamined Patent Publication No. Hei 2-200 can be cited. A vinylphosphonic acid-based compound described in Japanese Patent No. 25493 and the like. In addition, a compound containing a perfluoroalkyl group described in Japanese Patent Application Laid-Open No. 61-22048 can also be used. Furthermore, the "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984) can also be used as the introducer of the photopolymerizable monomer and oligomer.

In addition to the above, compounds represented by the following general formulae (MO-1) to (MO-5) can be preferably used. In the formula, when T is an oxyalkylene group, a carbon atom-side end is bonded to R.

[Chemical Formula 11]

[Chemical Formula 12]

In each of the above formulas, n is an integer of 0 to 14, and m is an integer of 0 to 8. A plurality of R and T in the molecule may be the same or different. In each of the compounds represented by the above formulae (MO-1) to (MO-5), at least one of the plurality of Rs is represented by -OC (= O) CH = CH ₂ or -OC (= O) C (CH ₃ ) = A group represented by CH ₂ . Specific examples of the compounds represented by the formulae (MO-1) to (MO-5) include compounds described in paragraphs 0248 to 0251 of Japanese Patent Application Laid-Open No. 2007-269779.

In addition, the following compounds described in Formula (1) and Formula (2) and their specific examples in Japanese Patent Application Laid-Open No. 10-62986 can also be used as radical polymerizable compounds, and the compounds are added to a polyfunctional alcohol A compound obtained by (meth) acrylated with ethylene oxide or propylene oxide. Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Laid-Open No. 2015-187211 can also be used as radical polymerizable compounds, and these contents are incorporated into this specification.

As the radical polymerizable compound, dipentaerythritol triacrylate (commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetraacrylate (commercially available product is KAYARAD D-320; Nippon Kayaku Co., Ltd., A-TMMT: Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (KAYARAD D-310 as a commercial product; Nippon Kayaku Co., Ltd. .), Dipentaerythritol hexa (meth) acrylate (available commercially as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.) and these A structure in which the (meth) acrylfluorenyl group is bonded via an ethylene glycol residue and a propylene glycol residue is preferable. It is also possible to use their oligo type. In addition, as a preferable example, pentaerythritol derivatives and / or dipentaerythritol derivatives of the above formula (MO-1) and (MO-2) may be mentioned. It is also possible to use SR209 manufactured by Sartomer company Inc.

The radical polymerizable compound may have an acid group such as a carboxyl group, a sulfo group, or a phosphate group. Examples of commercially available products include M-510 and M-520, which are polyacid-modified acrylic oligomers produced by TOAGOSEI CO., LTD. The preferable acid value of the radically polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, particularly preferably 5 to 30 mgKOH / g. When the acid value of the compound is in the above-mentioned range, the manufacturing and handling properties are excellent, and further the developability is excellent. Moreover, the radical polymerizability was favorable.

As the radical polymerizable compound, a compound having a caprolactone structure can also be used. The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, and trimethylol. Polypropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, trimethylol melamine, etc., and (meth) acrylic acid and ε-caprolactone esterified ε-hexane Lactone modified polyfunctional (meth) acrylate. Among them, a compound represented by the following formula (C) is preferable.

Formula (C) [Chemical Formula 13]

In the formula, 6 R are each a group represented by the following formula (D), or 1 to 5 of the 6 R are groups represented by the following formula (D), and the rest are represented by the following formula (D E) represents a group.

Formula (D) [Chemical Formula 14]

In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents 1 or 2, and "*" represents a bonding bond.

Formula (E) [Chemical Formula 15]

In the formula, R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bonding bond.

A compound having such a caprolactone structure is commercially available, for example, as KAYARAD DPCA series by Nippon Kayaku Co., Ltd. DPCA-20 (in the formulae (C) to (E) above, m = 1, The number of groups represented by formula (D) = 2, and R ¹ is a hydrogen atom compound), DPCA-30 (in the above formula, m = 1, the number of groups represented by formula (D) = 3, R ¹ is a compound of hydrogen atom), DPCA-60 (in the above formula, m = 1, the number of groups represented by formula (D) = 6, R ¹ is a compound of hydrogen atom), DPCA-120 ( In the above formula, m = 2, the number of groups represented by formula (D) = 6, a compound in which R ¹ is a hydrogen atom), and the like.

As the radical polymerizable compound, at least one selected from the group of compounds represented by the following general formula (i) or (ii) is also preferable.

[Chemical Formula 16]

In formulas (i) and (ii), E each independently represents-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-, and y each independently represents An integer of 0 to 10, and X each independently represents a (meth) acrylfluorenyl group, a hydrogen atom, or a carboxyl group. In formula (i), the total number of (meth) acrylfluorenyl groups is three or four, m each independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. However, when the total of each m is 0, any one of X is a carboxyl group. In the formula (ii), the total number of (meth) acrylfluorenyl groups is five or six, n each independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. However, when the total of each n is 0, any one of X is a carboxyl group.

In formula (i), m is preferably an integer of 0 to 6, and an integer of 0 to 4 is more preferred. In addition, the total of each m is preferably an integer of 2 to 40, an integer of 2 to 16 is more preferable, and an integer of 4 to 8 is particularly preferable. In formula (ii), n is preferably an integer of 0 to 6, and an integer of 0 to 4 is more preferred. In addition, the total of each n is preferably an integer of 3 to 60, an integer of 3 to 24 is more preferable, and an integer of 6 to 12 is particularly preferable. In formula (i) or (ii),-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-is the end of the oxygen atom side and X bond The shape is better. In particular, in formula (ii), a form in which all six X's are acrylfluorenyl is preferable.

Examples of commercially available compounds represented by the formulae (i) and (ii) include SR-494, Nippon Kayaku Co., which is a four-functional acrylate having four ethylene oxide chains, manufactured by Sartomer company Inc., Ltd. makes DPCA-60, which is a 6-functional acrylate having 6 pentene oxygen chains, TPA-330, which is a tri-functional acrylate having 3 isobutylene oxygen chains, and the like.

As the radically polymerizable compound, the aminomethyl compounds described in Japanese Patent Publication No. 48-41708, Japanese Patent Application Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765. Ester acrylates, as disclosed in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418. Urethane compounds based on a skeleton are also preferable. In addition, it is also possible to use an additive having an amine structure or a thioether structure in the molecule described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 1-105238. Form polymerizable monomers. Examples of commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd), NK ester M-40G, NK ester 4G, NK ester M-9300, NK Esters A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION.), And the like.

As the radical polymerizable compound, it is preferable to have a partial structure represented by the following formula from the viewpoint of heat resistance. Among them, * in the formula is a connection key.

[Chemical Formula 17]

Specific examples of the compound having the above partial structure include trimethylolpropane tri (meth) acrylate, isocyanurate ethylene oxide modified di (meth) acrylate, and isocyanurate ring. Ethylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (methyl) ) Acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, etc.

The content of the radical polymerizable compound in the resin composition is preferably 1 to 50% by mass based on the total solid content of the resin composition from the viewpoint of good radical polymerizability and heat resistance. The lower limit is more preferably 5 mass% or more. The upper limit is more preferably 30% by mass or less. The mass ratio of the polyimide precursor and the radical polymerizable compound (polyimide precursor / radical polymerizable compound) is preferably 98/2 to 10/90, and 95/5 to 30/70 More preferably, 90/10 to 50/50 is more preferable. If the mass ratio of a polyimide precursor and a radically polymerizable compound is the said range, a hardened film which is more excellent in hardenability and heat resistance can be formed. The radical polymerizable compound may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably within the above range.

<< Photoinitiator >> The resin composition in the present invention preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include a photocationic polymerization initiator, a photoradical polymerization initiator, and the like, and a photoradical polymerization initiator is preferred. The resin composition in the present invention contains a photoradical polymerization initiator, and after the resin composition is applied to a support such as a semiconductor wafer to form a resin composition layer, it is irradiated with light to cause hardening caused by radicals. This can reduce the solubility in the light irradiation section. Therefore, for example, there is an advantage that by exposing the resin composition layer through a light mask having a pattern that only shields the electrode portion, it is possible to easily create regions having different solubility depending on the pattern of the electrode or the like.

The photopolymerization initiator is not particularly limited, and can be appropriately selected from known photopolymerization initiators. For example, a photopolymerization initiator having sensitivity to light from the ultraviolet region to the visible region is preferred. In addition, it may be an active agent which generates a certain action with a photo-excited sensitizer and generates an active radical. The photopolymerization initiator preferably contains at least one compound having a Molar absorption coefficient of at least about 50 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of a compound can be measured by a well-known method. For example, it is preferable to use an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Corporation) and use ethyl acetate solvent to measure at a concentration of 0.01 g / L.

As the photopolymerization initiator, a known compound can be arbitrarily used. Examples include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl skeleton), fluorenylphosphine compounds such as fluorenylphosphine oxide, and hexaarylbisazole Oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, Metallocene compounds, organic boron compounds, iron aromatic hydrocarbon complexes, and the like. Regarding these details, refer to the descriptions in paragraphs 0165 to 0182 of Japanese Patent Application Laid-Open No. 2016-027357 and incorporate the contents into this specification. In addition, as the ketone compound, for example, a compound described in paragraph 0087 of Japanese Patent Application Laid-Open No. 2015-087611 can be exemplified, and the content is incorporated into the present specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

As the photopolymerization initiator, an α-hydroxyketone compound, an α-amino ketone compound, a fluorenylphosphine compound, and a metallocene compound can also be preferably used. More specifically, for example, a photopolymerization initiator described in Japanese Patent Application Laid-Open No. 10-291969 and a photopolymerization initiator described in Japanese Patent No. 4225898 can also be used. As the α-hydroxy ketone compound, IRGACURE-184 (IRGACURE is a registered trademark), DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF Corporation) can be used. As the α-amino ketone compound, commercially available IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Corporation) can be used. As the α-amino ketone compound, a compound described in Japanese Patent Application Laid-Open No. 2009-191179 can be used in which the absorption maximum wavelength matches a wavelength light source such as 365 nm or 405 nm. Examples of the fluorenylphosphine compound include 2,4,6-trimethylbenzylfluorenyl-diphenyl-phosphine oxide and the like. In addition, IRGACURE-819 or IRGACURE-TPO (trade name: both manufactured by BASF) can be used as commercially available products. Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

The photopolymerization initiator is more preferably an oxime compound. By using an oxime compound, exposure latitude can be improved more effectively. The oxime compound has a wide exposure latitude (exposure margin) and also functions as a hot alkali generator, so it is particularly preferable. As specific examples of the oxime compound, a compound described in JP 2001-233842, a compound described in JP 2000-80068, and a compound described in JP 2006-342166 can be used. . Preferred oxime compounds include, for example, 3-benzyloxyiminobutane-2-one, 3-ethoxyiminobutane-2-one, and 3-propanyloxyimine Aminobutane-2-one, 2-acetaminoiminopentane-3-one, 2-acetaminoimino-1-phenylpropane-1-one, 2-benzidine Oxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1 -Phenylpropane-1-one and the like.

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are made by BASF), ADEKA OPTOMER N-1919 (made by ADEKA Corporation, Japanese Patent Application Laid-Open No. 2012-14052) Photopolymerization initiator 2) described in the publication. In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. DFI-091 (DAITO (Manufactured by CHEMIX Co., Ltd.). Further, an oxime compound having a fluorine atom can be used. Specific examples of such an oxime compound include the compounds described in Japanese Patent Application Laid-Open No. 2010-262028, and Japanese Patent Application No. 2014 Compounds 24, 36 to 40 described in paragraph 0345 of Japanese Patent Publication No. -500852, and compounds (C-3) described in paragraph 0101 of Japanese Patent Application Laid-Open No. 2013-164471. Examples of the best oxime compound include An oxime compound having a specific substituent shown in Japanese Patent Application Laid-Open No. 2007-269779, an oxime compound having a sulfur aryl group shown in Japanese Patent Application Laid-Open No. 2009-191061, and the like.

As the photopolymerization initiator, from the viewpoint of exposure sensitivity, it is selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, and fluorenylphosphine compounds. , Phosphine oxide compound, metallocene compound, oxime compound, triarylimidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene- At least one of an iron complex and a salt thereof, a halomethyloxadiazole compound, and a 3-aryl substituted coumarin compound is preferably selected from the group consisting of a trihalomethyltriazine compound, an α-hydroxyketone compound, α -At least one of an amino ketone compound, a fluorenyl phosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, and an acetophenone compound is more preferable At least one selected from the group consisting of trihalomethyltriazine compound, α-hydroxyketone compound, α-amino ketone compound, oxime compound, triarylimidazole dimer and benzophenone compound is further preferred, and the metallocene Compound An oxime compound is further preferred, and an oxime compound is particularly preferred.

As the photopolymerization initiator, N, N'-tetraane such as benzophenone and N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone) can be used. -4,4'-diaminobenzophenone; 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1, 2-methyl- Aromatic ketones such as 1- [4- (methylthio) phenyl] -2-morpholinyl-acetone-1; quinones formed by condensation with aromatic rings such as alkyl anthraquinone; benzoin alkyl ethers, etc. Benzoin compounds such as benzoin ether compounds, benzoin and alkyl benzoin; benzoin derivatives such as benzoin dimethyl ketal and the like. A compound represented by the following formula (I) can also be used. [Chemical Formula 18] In formula (I), R ⁵⁰ is an alkyl group having 1 to 20 carbon atoms; an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms; an alkoxy group having 1 to 12 carbon atoms; phenyl group; carbon number 1 to 20 alkyl groups, 1 to 12 alkoxy groups, halogen atoms, cyclopentyl, cyclohexyl, 2 to 12 alkenyl groups, and 2 to 18 carbon atoms interrupted by one or more oxygen atoms An alkyl group and a phenyl group substituted with at least one of alkyl groups having 1 to 4 carbon atoms; or a biphenyl group, R ⁵¹ is a group represented by formula (II), or a group identical to R ⁵⁰ , R ⁵² to R ⁵⁴ are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen. [Chemical Formula 19] Formula (II) In the formula, R ⁵⁵ to R ⁵⁷ are the same as R ⁵² to R ^{54 in} the formula (I).

As the photopolymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. WO2015 / 125469 can also be used.

The content of the photopolymerization initiator is preferably 0.1 to 30% by mass based on the total solid content of the resin composition, more preferably 0.1 to 20% by mass, and still more preferably 0.1 to 10% by mass. The photopolymerization initiator may contain only one kind, or may contain two or more kinds. When two or more kinds of photopolymerization initiators are contained, the total amount thereof is preferably in the above range.

<<< polymerization inhibitor> It is preferable that the resin composition in the present invention contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-third-butyl-p-cresol, catechol, p-third-butylcatechol, p- Benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis (3-methyl-6-third butylphenol), 2,2'-methylenebis (4-methyl-6 -Third butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-third-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamine) phenol, N-nitroso -N- (1-naphthyl) hydroxylamine ammonium salt, bis (4-hydroxy-3,5-third butyl) phenylmethane and the like. In addition, the polymerization inhibitors described in paragraph 0060 of Japanese Patent Laid-Open No. 2015-127817 and the compounds described in paragraphs 031 to 0046 of International Publication No. WO2015 / 125469 can also be used.

When the resin composition has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass based on the total solid content of the resin composition. The polymerization inhibitor may be only one kind, or two or more kinds. When there are two or more kinds of polymerization inhibitors, the total is preferably in the above range.

<<< Photobase generator> The resin composition in this invention may contain a photobase generator. The photo-alkali generator is one that generates alkali by exposure and does not show activity under normal conditions of normal temperature and pressure. However, if it is an external stimulus when it is irradiated with electromagnetic waves and heated, it generates alkali (alkaline substance). There is no particular limitation.

The content of the photobase generator is not particularly limited as long as it can form a desired pattern, and it can be set to a normal content. The content of the photobase generator is preferably in a range of 0.01 parts by mass or more and less than 30 parts by mass based on 100 parts by mass of the resin composition, more preferably in a range of 0.05 parts by mass to 25 parts by mass, and more preferably 0.1 part by mass. The range of -20 mass parts is more preferable.

In the present invention, a known compound can be used as the photobase generator. For example, M. Shirai, and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Masahiro Kakuoka, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev., 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci.Technol., 13,153 (2000); M. Winkle, and K. Graziano, J. Photopolym. Sci. Technol., 3,419 (1990); M. Tsunooka, H. Tachi, and S. Yoshitaka, J. Photopolym. Sci. Technol., 9, 13 (1996); K. Suyama, H. Araki, M. Shirai, J. Photopolym. Sci. Technol., 19, 81 (2006), such as complexes of transition metal compounds Those with structures such as ammonium salts, such as those whose amidine is partially potentialized by forming salts with carboxylic acids, ionic compounds, carbamate derivatives, and oxime ester derivatives whose alkali components are neutralized due to salt formation , Fluorenyl compounds, etc. Nonionic compounds in which the alkali component is potentially converted by a urethane bond or an oxime bond. It is also preferable to use WPBG-266 (manufactured by Wako Pure Chemical Industries, Ltd.).

The basic substance produced by the photobase generator is not particularly limited, and examples thereof include compounds having an amine group, and in particular, polyamines such as monoamines and diamines, and fluorene. The produced basic substance is preferably a compound having an amine group having a higher basicity. The reason for this is that the catalyst effect on the dehydration condensation reaction during the polyimide precursor of the polyimide precursor is strong, and a small amount can be added to show the catalyst effect on the dehydration condensation reaction and the like at a lower temperature. That is, since the generated alkaline substance has a large catalyst effect, the sensitivity of the appearance as a resin composition is improved. From the viewpoint of the catalyst effect, fluorene and aliphatic amine groups are preferred.

The photobase generator is preferably a photobase generator that does not include a salt in the structure. It is preferable that the nitrogen atom in the alkali portion generated in the photobase generator has no charge. In the photobase generator, the generated base is potentially made better by using a covalent bond, and the covalent bond between the base generating mechanism and the atom adjacent to the nitrogen atom of the generated base portion is Compounds which are cleaved to produce a base are more preferred. If the photobase generator does not contain a salt in the structure, the photobase generator can be neutralized, so the solvent solubility is good, and the pot life is improved. For this reason, it is preferable that the amine generated from the photobase generator used in the present invention is a primary amine or a secondary amine.

In addition, for the reasons described above, it is preferable that the base generated as described above is potentially converted to a covalent bond in the photobase generator. Further, the generated base is more preferably converted to a amide bond, a urethane bond, or an oxime bond.

As the photobase generator, a photobase generator having a cinnamic acid ammonium structure described in Japanese Patent Application Laid-Open No. 2009-80452 and International Publication WO2009 / 123122, Japanese Patent Application Laid-Open No. 2006-189591, and Japan can also be used. A photobase generator having a carbamate structure described in JP 2008-247747, a oxime ester structure described in JP 2007-249013 and JP 2008-003581, Photobase generator of carbamoxime structure.

In addition, examples of the photobase generator include compounds described in paragraphs 0185 to 0188, 0199 to 0200, and 0202 of Japanese Patent Laid-Open No. 2012-93746, and paragraphs 0022 to 0069 of Japanese Patent Laid-Open No. 2013-194205. Compounds described in paragraphs, compounds described in paragraphs 0026 to 0074 of Japanese Patent Application Laid-Open No. 2013-204019, and compounds described in paragraph 0052 of WO2010 / 064631.

<<< Thermal alkali generator> The resin composition in this invention may contain a thermal alkali generator. The hot alkali generator preferably contains at least one selected from the group consisting of an acidic compound (A1) that generates a base when heated to 40 ° C or higher, and an ammonium salt (A2) of an anion and ammonium cation having pKa1 of 0 to 4. Here, pKa1 represents the logarithmic display (-Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the polyacid. The acidic compound (A1) and the ammonium salt (A2) are those that generate a base upon heating. Therefore, the cyclization reaction of a polyimide precursor and the like can be promoted by the base generated from these compounds, and can be used at low temperatures. Cyclization of polyimide precursors and the like is performed. Moreover, even if these compounds coexist with polyimide precursors and the like which are cyclized and hardened by an alkali, cyclization of polyimide precursors and the like hardly proceed without heating, so that they can be prepared and stored stably. Resin composition with excellent properties. In addition, in the present specification, an acidic compound refers to a compound having a pH value of less than 7 measured at 20 ° C using a pH meter. The solution is obtained by collecting 1 g of the compound into a container, and adding 50 mL of ion-exchanged water and tetrahydrofuran. The mixed solution (mass ratio: water / tetrahydrofuran = 1/4) was stirred at room temperature for 1 hour to obtain a solution.

The alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C or higher, and more preferably 120 to 200 ° C. The upper limit of the alkali generation temperature is more preferably 190 ° C or lower, more preferably 180 ° C or lower, and even more preferably 165 ° C or lower. The lower limit of the alkali generation temperature is more preferably 130 ° C or more, and more preferably 135 ° C or more. If the alkali generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C or higher, it is difficult to generate an alkali during storage, so that a resin composition having excellent stability can be prepared. When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200 ° C or lower, the cyclization temperature of the polyfluorene imide precursor and the like can be reduced. The alkali generation temperature can be measured, for example, by using differential scanning calorimetry to heat the compound to 250 ° C at 5 ° C / min in a pressure-resistant capsule, and read the peak temperature of the lowest temperature exothermic peak, and The temperature is taken as the alkali generation temperature.

The alkali-based secondary amine or tertiary amine generated by the hot alkali generator is more preferable, and the tertiary amine is more preferable. Tertiary amines have high basicity, and therefore can further reduce the cyclization temperature of polyimide precursors and the like. The boiling point of the alkali generated by the hot alkali generator is preferably 80 ° C or higher, more preferably 100 ° C or higher, and most preferably 140 ° C or higher. The molecular weight of the generated base is preferably 80 to 2,000. The lower limit is more preferably 100 or more. The upper limit is preferably 500 or less. In addition, the molecular weight value is a theoretical value calculated | required from a structural formula.

The acidic compound (A1) preferably contains one or more selected from an ammonium salt and a compound represented by the formula (A1) described later.

The ammonium salt (A2) -based acidic compound is preferred. In addition, the above-mentioned ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40 ° C or higher (preferably 120 to 200 ° C), or may be a compound other than heated to 40 ° C or higher (preferably 120 to 200) ℃) to produce compounds other than the acidic compounds of the base.

In the present invention, the ammonium salt refers to a salt of an ammonium cation and an anion represented by the following formula (101) or formula (102). The anion may be bonded to any part of the ammonium cation through a covalent bond, and may also be provided outside the molecule of the ammonium cation, and it is preferably provided outside the molecule of the ammonium cation. In addition, having an anion outside the molecule of the ammonium cation means a case where the ammonium cation and the anion are not bonded by a covalent bond. Hereinafter, the anion outside the molecule of the cation part is called a counter anion. [Chemical Formula 20] In the above formula, R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and the formula R ⁷ represents a hydrocarbon group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁵ and R ⁷ may be bonded to form a ring, respectively.

In the present invention, it is preferable that the ammonium salt has an anion and an ammonium cation having a pKa1 of 0 to 4. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, and even more preferably 3.2 or less. The lower limit is more preferably 0.5 or more, and more preferably 1.0 or more. When the pKa1 of the anion is within the above range, the polyfluorene imide precursor and the like can be cyclized at a low temperature, and the stability of the resin composition can be improved. When pKa1 is 4 or less, the stability of the hot alkali generator is good, the generation of alkali without heating can be suppressed, and the stability of the resin composition is good. When pKa1 is 0 or more, the generated base is not easily neutralized, and the cyclization efficiency of the polyfluorene imide precursor and the like is good. The type of the anion is preferably one selected from the group consisting of a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and a carboxylate anion is more preferable from the viewpoint of having both the stability of a salt and the thermal decomposition property. That is, an ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion. The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and more preferably an anion of a divalent carboxylic acid. According to this aspect, it can be set as the hot alkali generator which can further improve the stability, hardenability, and developability of a resin composition. In particular, by using an anion of a divalent carboxylic acid, the stability, curability, and developability of the resin composition can be further improved. In the present invention, an anion of a carboxylic acid having a carboxylate anion-based pKa1 of 4 or less is preferred. pKa1 is preferably 3.5 or less, and more preferably 3.2 or less. According to this aspect, the stability of the resin composition can be further improved. Among them, pKa1 represents the logarithm of the inverse of the first dissociation constant of the acid, and can refer to Determination of Organic Structures by Physical Methods (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod , FC; Editors: Braude, EA, Nachod, FC; Academic Press, New York, 1955), and Data for Biochemical Research (Physical Identification of Organic Structures) (Author: Dawson, RMCet al; Oxford, Clarendon Press, 1959 ). For compounds not described in these documents, the values calculated by the structural formula using software using ACD / pKa (manufactured by ACD / Labs) were used.

In the present invention, the carboxylate anion is preferably represented by the following formula (X1). [Chemical Formula 21] In the formula (X1), EWG represents an electron withdrawing group.

In the present invention, the electron-withdrawing group means that the substituent constant σm of Hammett represents a positive value. Among them, σm Yu Tatsuo's general theory, "The Journal of the Society of Organic Synthetic Chemistry" Vol. 23 No. 8 (1965) pages 631-642 are described in detail. The electron-withdrawing group of the present invention is not limited to the substituents described in the aforementioned documents. Examples of substituents in which σm represents a positive value include CF ₃ group (σm = 0.43), CF ₃ CO group (σm = 0.63), HC≡C group (σm = 0.21), and CH ₂ = CH group (σm = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCOCH = CH group (σm = 0.21), PhCO group (σm = 0.34), H ₂ NCOCH ₂ group (σm = 0.06), etc. In addition, Me represents a methyl group, Ac represents an ethenyl group, and Ph represents a phenyl group.

In the present invention, EWG is preferably a group represented by the following formulae (EWG-1) to (EWG-6). [Chemical Formula 22] In the formula, R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group, or a carboxyl group, and Ar represents an aryl group.

In the present invention, it is also preferable that the carboxylate anion is represented by the following formula (X). [Chemical Formula 23] In the formula (X), L ¹⁰ represents a single bond or a divalent linking group selected from the group consisting of an alkylene group, an alkenyl group, an arylene group, -NR ^X- , and a combination thereof, and R ^X represents a hydrogen atom, an alkyl group, Alkenyl or aryl.

Specific examples of the carboxylate anion include a maleate anion, a phthalate anion, an N-phenylimide diacetate anion, and an oxalate anion. These can be preferably used.

The ammonium cation is preferably represented by any one of the following general formulae (Y1-1) to (Y1-6). [Chemical Formula 24]

In the above general formula, R ¹⁰¹ represents an n-valent organic group, R ¹⁰² to R ¹¹¹ each independently represent a hydrogen atom or a hydrocarbon group, R ¹⁵⁰ and R ¹⁵¹ each independently represent a hydrocarbon group, R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ and R ¹⁵⁰ R ¹⁰⁷ and R ¹⁰⁸ and R ¹⁰⁹ and R ¹¹⁰ may be bonded to each other to form a ring. Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group, n represents an integer of 1 or more, and m represents an integer of 0 to 5.

R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ and R ¹⁵⁰ , R ¹⁰⁷ and R ^108, and R ¹⁰⁹ and R ¹¹⁰ may be bonded to each other to form a ring. Examples of the ring include an aliphatic ring (non-aromatic hydrocarbon ring), an aromatic ring, and a heterocyclic ring. Rings can be monocyclic or polycyclic. Examples of the linking group when a ring is formed by the above-mentioned group bonding include a group selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aryl group, and combinations thereof. 2-valent link base. Specific examples of the formed ring include a pyrrolidine ring, a pyrrole ring, a piperidine ring, a pyridine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a pyrazine ring, a morpholine ring, and a thiazine. Ring, indole ring, isoindole ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, perylene ring, carbazole ring, and the like.

In the present invention, the ammonium cation is preferably a structure represented by formula (Y1-1) or formula (Y1-2), is represented by formula (Y1-1) or formula (Y1-2), and R ¹⁰¹ is an aryl group The structure is more preferable, which is represented by formula (Y1-1), and the structure of the R ^101- based aryl group is particularly preferable. That is, in the present invention, the ammonium cation is more preferably represented by the following formula (Y). [Chemical Formula 25] In formula (Y), Ar ¹⁰ represents an aromatic group, R ¹¹ to R ¹⁵ each independently represent a hydrogen atom or a hydrocarbon group, R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring, and n represents an integer of 1 or more.

R ¹¹ and R ¹² each independently represent a hydrogen atom or a hydrocarbon group. The hydrocarbon group is not particularly limited, and an alkyl group, an alkenyl group or an aryl group is preferred. R ¹¹ and R ¹² are more preferably a hydrogen atom.

R ¹³ to R ^{15 each} represent a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include the hydrocarbon groups described with reference to R ¹¹ and R ¹² . R ¹³ to R ^{15 are} particularly preferably an alkyl group, and the preferred aspects are the same as those described with R ¹¹ and R ¹² .

R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. Examples of the ring include a cyclic aliphatic (non-aromatic hydrocarbon ring), an aromatic ring, and a heterocyclic ring. Rings can be monocyclic or polycyclic. Examples of the linking group when R ¹⁴ and R ^{15 are} bonded to form a ring include a group selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group, and combinations thereof. The bivalent link base. Specific examples of the formed ring include a pyrrolidine ring, a pyrrole ring, a piperidine ring, a pyridine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a pyrazine ring, a morpholine ring, and a thiazine. Ring, indole ring, isoindole ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, perylene ring, carbazole ring, and the like.

Among R ¹³ to R ¹⁵ , R ¹⁴ and R ¹⁵ are bonded to each other to form a ring, or R ¹³ is a linear alkyl group having 5 to 30 carbon atoms (more preferably 6 to 18 carbon atoms), and R ¹⁴ and R ¹⁵ are respectively An alkyl group independently having 1 to 3 carbon atoms (more preferably 1 or 2 carbon atoms) is preferred. According to this aspect, it is possible to easily produce amine species having a high boiling point. From the viewpoint of the basicity or boiling point of the amine species to be generated, the total number of carbon atoms of R ¹³ , R ¹⁴ and R ¹⁵ is preferably 7 to 30, and more preferably 10 to 20. In addition, from the reason that amine species having a high boiling point are easily generated, the amount of the chemical formula of "-NR ¹³ R ¹⁴ R ¹⁵ " in the formula (Y) is preferably 80 to 2000, and more preferably 100 to 500.

Further, as an embodiment for further improving the adhesion with a metal layer such as copper, in the formula (Y), R ¹³ and R ¹⁴ are methyl or ethyl groups, and R ¹⁵ is a direct group having 5 or more carbon atoms. A chain, branch, or cyclic alkyl group is in the form of an aryl group. R ¹³ and R ¹⁴ are methyl groups, R ¹⁵ is a linear alkyl group having 5 to 20 carbon atoms, a branched alkyl group having 6 to 17 carbon atoms, a cyclic alkyl group having 6 to 10 carbon atoms or a phenyl group, R ¹³ and R ¹⁴ are methyl groups, and R ¹⁵ is preferably a linear alkyl group having 5 to 10 carbon atoms, a branched alkyl group having 6 to 10 carbon atoms, a cyclic alkyl group having 6 to 8 carbon atoms, or a phenyl group. By reducing the hydrophobicity of the amine species in this way, even when the amine is adhered to a metal layer such as copper, the affinity between the metal layer and polyfluorene is improved.

In the present invention, an acidic compound is also preferably a compound represented by the following formula (A1). The compound is acidic at room temperature, and the carboxyl group is decarbonated or dehydrated and cyclized by heating to disappear, whereby the previously neutralized and passivated amine site becomes active, thereby becoming alkaline. Expression (A1) will be described below.

Formula (A1) [Chemical Formula 26] In Formula (A1), A ¹ represents a p-valent organic group, R ¹ represents a mono-valent organic group, L ¹ represents a (m + 1) -valent linking group, m represents an integer of 1 or more, and p represents an integer of 1 or more.

In the formula (A1), A ¹ represents a p-valent organic group. Examples of the organic group include an aliphatic group and an aromatic group. An aromatic group is preferred. By making A ^{1 an} aromatic group, a base with a high boiling point can be easily produced at a lower temperature. By increasing the boiling point of the generated base, the polyimide precursor can be suppressed from being volatilized or decomposed by heating during hardening, and the cyclization of the polyimide precursor can be performed more effectively. Examples of the monovalent aliphatic group include an alkyl group and an alkenyl group. The carbon number of the alkyl group is preferably from 1 to 30, more preferably from 1 to 20, and even more preferably from 1 to 10. The alkyl group may be any of linear, branched, and cyclic. The alkyl group may have a substituent or may be unsubstituted. Specific examples of the alkyl group include methyl, ethyl, third butyl, dodecyl, cyclopentyl, cyclohexyl, cycloheptyl, and adamantyl. The carbon number of the alkenyl group is preferably 2 to 30, more preferably 2 to 20, and even more preferably 2 to 10. The alkenyl group may be any of linear, branched, and cyclic. The alkenyl group may have a substituent or may be unsubstituted. Examples of the alkenyl group include a vinyl group and a (meth) allyl group. Examples of the divalent or higher aliphatic group include a group obtained by removing one hydrogen atom from the monovalent aliphatic group. The aromatic group may be monocyclic or polycyclic. The aromatic group may be an aromatic heterocyclic group containing a hetero atom. The aromatic group may have a substituent or may be unsubstituted. Unsubstituted is better. Specific examples of the aromatic group include a benzene ring group, a naphthalene ring group, a pentalene ring group, an indenyl ring group, a fluorenyl ring group, a heptene ring group, an indenene ring group, a fluorenyl ring group, and a condensed pentaphenyl group. Ring group, pinene ring group, phenanthrene ring group, anthracene ring group, fused tetraphenyl ring group, fluorene ring group, triphenylene ring group, fluorene ring group, biphenyl ring group, pyrrole ring group, furan ring group, thiophene Ring group, imidazole ring group, oxazole ring group, thiazole ring group, pyridine ring group, pyrazine ring group, pyrimidine ring group, pyridazine ring group, indazine ring group, indole ring group, benzofuran ring group , Benzothiophene ring, isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline Ring group, carbazole ring group, morphinyl ring group, acridine ring group, phenanthroline ring group, thienthyl ring group, benzopyran ring group, xanthene ring group, phenoxaline group, phenothiazine ring And phenazine ring, benzene ring is the best. The aromatic group may have a plurality of aromatic rings connected via a single bond or a linking group described later. As the linking group, for example, an alkylene group is preferred. It is also preferable that the alkylene group is any of a linear chain and a branch. Specific examples of the group in which a plurality of aromatic rings are connected via a single bond or a linking group include biphenyl, diphenylmethane, diphenylpropane, diphenylisopropyl, and triphenylmethane. Group, tetraphenylmethane and the like.

Examples of the substituent which may have an organic group represented by A ¹ include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; and alkoxy groups such as a methoxy group, an ethoxy group, and a third butoxy group. Aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl; aryloxycarbonyl groups such as phenoxycarbonyl; ethoxyl, propyloxy, and Benzyloxy, such as benzyloxy; ethynyl, benzyl, isobutylfluorenyl, acrylfluorenyl, methacryl, and methoxysulfenyl; methylmercapto and tertiary butylmercapto Alkyl mercapto groups; aryl mercapto groups such as phenyl mercapto and p-tolyl mercapto; alkyl groups such as methyl, ethyl, third butyl, and dodecyl; halogenated alkyl groups such as fluorinated alkyl; cyclopentyl, Cycloalkyl groups such as cyclohexyl, cycloheptyl, and adamantyl; aryl groups such as phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthracenyl, and phenanthryl; hydroxyl; carboxyl; Sulfo; cyano; alkylaminocarbonyl; arylaminocarbonyl; sulfoamido; silyl; amino; monoalkylamino; dialkylamino; aryl Group; diaryl group; sulfoxy; or combinations thereof.

L ¹ represents a (m + 1) -valent linking group. The linking group is not particularly limited, and examples include -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO _2- , and alkylene (preferably having 1 carbon number) ~ 10 straight or branched alkylene), cycloalkyl (preferably a cycloalkyl having 3 to 10 carbon atoms), alkenyl (preferably a linear or branched alkylene having 210 carbon atoms) ) Or a linking base formed by connecting a plurality of them. The total carbon number of the linking group is preferably 3 or less. The linking group is preferably alkylene, cycloalkylene, or alkylene, linear or branched alkylene is more preferred, linear alkylene is further preferred, or ethylene or methylene is particularly preferred. Methylene is the best.

R ¹ represents a monovalent organic group. Examples of the monovalent organic group include an aliphatic group and an aromatic group. Examples of the aliphatic group and the aromatic group include those described above with reference to A ¹ . The monovalent organic group represented by R ¹ may have a substituent. Examples of the substituent include the above. R ¹ is preferably a group having a carboxyl group. That is, R ¹ is preferably a group represented by the following formula. -L ² - (COOH) _n in the formula, L ² represents a (n + 1) divalent linking group, n represents an integer of 1 or more. Regarding the linking group represented by L ² , the groups described above with reference to L ¹ may be mentioned, and the preferred ranges are also the same. Ethylene or methylene is particularly preferred, and methylene is most preferred. n represents an integer of 1 or more, 1 or 2 is preferable, and 1 is more preferable. The upper limit of n is the maximum number of substituents which can be adopted for the linking group represented by L ² . When n is 1, a tertiary amine having a high boiling point is easily generated by heating at 200 ° C or lower. Furthermore, the stability of a resin composition can be improved.

m represents an integer of 1 or more, 1 or 2 is preferable, and 1 is more preferable. The upper limit of m is the maximum number of substituents that the linking group represented by L ¹ can adopt. When m is 1, a tertiary amine having a high boiling point is easily generated by heating at 200 ° C or lower. Furthermore, the stability of a resin composition can be improved. p represents an integer of 1 or more, 1 or 2 is preferable, and 1 is more preferable. The upper limit of p is the maximum number of substituents that can be used for the organic group represented by A ¹ . When p is 1, a tertiary amine having a high boiling point is easily generated by heating at 200 ° C or lower.

In the present invention, the compound represented by the formula (A1) is preferably a compound represented by the following formula (1a). [Chemical Formula 27] In formula (1a), A ¹ represents a p-valent organic group, L ¹ represents a (m + 1) -valent linking group, L ² represents a (n + 1) -valent linking group, m represents an integer of 1 or more, and n represents an integer of 1 or more. Integer, p represents an integer of 1 or more. The definitions of A ¹ , L ¹ , L ² , m, n, and p in the general formula (1a) are the same as those described in the general formula (A1), and the preferable ranges are also the same.

In the present invention, the compound represented by the formula (A1) is preferably N-aryliminodiacetic acid. N-aryliminodiacetic acid is a compound in which A ¹ in the general formula (A1) is an aromatic group, L ¹ and L ² are a methylene group, m is 1, n is 1, and p is 1. N-aryliminodiacetic acid easily produces tertiary amines with a high boiling point at 120-200 ° C.

Hereinafter, specific examples of the hot alkali generator are described, but the present invention is not limited thereto. These may be used individually or in mixture of 2 or more types. Me in the following formula represents a methyl group. Among the compounds shown below, (A-1) to (A-11), (A-18), and (A-19) are compounds represented by the above formula (A1). Among the compounds shown below, (A-1) to (A-11), (A-18) to (A-26) are more preferable, and (A-1) to (A-9), (A-18) ) ~ (A-21), (A-23), (A-24) are further preferred.

[Table 1]

[Table 2] [table 3] [Table 4] [table 5]

As the hot alkali generator used in the present invention, the compounds described in paragraphs 0015 to 0055 of the specification of Japanese Patent Application No. 2015-034388 can also be preferably used and incorporated into this specification.

When a hot alkali generator is used, the content of the hot alkali generator in the resin composition is preferably 0.1 to 50% by mass based on the total solid content of the resin composition. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. As the hot alkali generator, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.

<<< Thermal radical polymerization initiator> The resin composition in this invention may contain a thermal radical polymerization initiator. As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used. The thermal radical polymerization initiator is a compound that generates a radical by thermal energy and initiates or accelerates a polymerization reaction such as a polymerizable compound. By adding a thermal radical polymerization initiator, when a cyclization reaction such as a polyfluorene imide precursor is performed, a polymerization reaction such as a polymerizable compound can be performed. When the polyfluorene imide precursor contains a radical polymerizable group, the polymerization reaction of the polyfluorene imide precursor can be performed simultaneously with the cyclization of the polyfluorene imide precursor, and therefore, higher heat resistance can be achieved. Examples of the thermal radical polymerization initiator include aromatic ketones, onium salt compounds, peroxides, sulfur compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azineium compounds, and metallocenes Compounds, active ester compounds, compounds having carbon-halogen bonds, azo compounds, and the like. Among them, a peroxide or an azo compound is more preferable, and a peroxide is particularly preferable. The 10-hour half-life temperature of the thermal radical polymerization initiator used in the present invention is preferably 90 to 130 ° C, and more preferably 100 to 120 ° C. Specifically, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Laid-Open No. 2008-63554 can be cited. Among commercially available products, PERBUTYL Z and PERCUMYL D (manufactured by NOF CORPORATION.) Can be preferably used.

When the resin composition contains a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator is preferably 0.1 to 50% by mass, and more preferably 0.1 to 30% by mass relative to the total solid content of the resin composition. 0.1 to 20% by mass is particularly preferred. The thermal radical polymerization initiator is preferably contained in an amount of 0.1 to 50 parts by mass based on 100 parts by mass of the polymerizable compound, and more preferably contained in an amount of 0.5 to 30 parts by mass. According to this aspect, a cured film having more excellent heat resistance is easily formed. The thermal radical polymerization initiator may be only one kind, or two or more kinds. When there are two or more types of thermal radical polymerization initiators, it is preferable that the total is in the above range.

<<< Antirust agent> It is preferable that the resin composition in this invention contains an antirust agent. The resin composition contains a rust inhibitor, thereby effectively inhibiting metal ions originating from the metal layer (metal wiring) from moving into the resin composition layer. As the rust inhibitor, the rust inhibitor described in paragraph 0094 of Japanese Patent Application Laid-Open No. 2013-15701, the compound described in paragraphs 0073 to 0076 of Japanese Patent Application Laid-Open No. 2009-283711, and Japanese Patent Application Laid-Open No. 2011- Compounds described in paragraph 0052 of Japanese Patent No. 59656, compounds described in paragraphs 0114, 0116, and 0118 of Japanese Patent Application Laid-Open No. 2012-194520. Specific examples include a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridine). Compounds such as hydrazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and thiol groups, Hindered phenolic compounds, salicylic acid derivative compounds, hydrazine derivative compounds. Among them, triazole compounds such as triazole and benzotriazole, and tetrazole compounds such as tetrazole and benzotetrazole are preferred, and 1,2,4-triazole and 1,2,3-benzotriazole 5-methyl-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-tetrazole are more preferred, and 1H-tetrazole is most preferred. Examples of commercially available products include KEMITEC BT-C (made by CHEMIPRO KASEI KAISHA, LTD, 1,2,3-benzotriazole), 1HT (made by TOYOBO CO., LTD., 1H-tetrazole), and P5T (TOYOBO CO., LTD., 5-phenyl-1H-tetrazole). It is also preferable to use KEMINOX 179 (manufactured by CHEMIPRO KASEI KAISHA, LTD).

When the resin composition contains a rust preventive agent, the content of the rust preventive agent is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the resin, and more preferably 0.2 to 5 parts by mass. The rust inhibitor may be only one kind, or two or more kinds. When two or more kinds are used, it is preferable that the total is in the above range.

<< Silane coupling agent It is preferable that the resin composition in the present invention may contain a silane coupling agent for improving the adhesion with a metal material used for an electrode, a wiring, or the like. Examples of the silane coupling agent include compounds described in paragraphs 0061 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication WO2011 / 080992A1, and Japanese Patent Laid-Open No. 2014- The compounds described in paragraphs 0060 to 0061 of 191252, the compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-41264, and the compounds described in paragraph 0055 of international publication WO2014 / 097594. As described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358, it is also preferable to use two or more different silane coupling agents. As the silane coupling agent, 2-((3- (triethoxysilyl) propyl) aminomethylamido) benzoic acid, triethoxysilylpropylmaleic acid, and the following Compounds are also preferred. In the following formula, Et represents an ethyl group. As a commercially available product, KBM-602 (manufactured by Shin-Etsu Chemical Co., Ltd., N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane) and the like can also be used. [Chemical Formula 28]

The silane coupling agent is preferably in the range of 0.1 to 30 parts by mass, and more preferably in the range of 0.5 to 15 parts by mass based on 100 parts by mass of the resin. By setting the content of the silane coupling agent to 0.1 parts by mass or more, the adhesion to the metal layer of the obtainable film is improved, and by setting the content of the silane coupling agent to 30 parts by mass or less, The film has good heat resistance and physical properties. The silane coupling agent may be only one kind, or two or more kinds. When two or more kinds are used, it is preferable that the total is in the above range.

<< Solvent> In the present invention, when the resin composition is formed into a layer by coating, it is preferable to mix the solvent with the resin composition. As the solvent, a known solvent can be arbitrarily used. Examples include compounds such as esters, ethers, ketones, aromatic hydrocarbons, and fluorenes. Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and the like. Butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (eg, methyl alkoxyacetate, alkoxy Ethyl acetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) ), Alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, 3 -Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (for example, 2-alkoxy Methyl propionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 -Propyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2- Methyloxy-2-methylpropanoate and ethyl 2-alkoxy-2-methylpropanoate (eg, methyl 2-methoxy-2-methylpropionate, 2-ethoxy- 2-methyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutanoate, 2-oxo On behalf of ethyl butyrate. Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl cellosolve acetate. , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Esters, etc. Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone. Examples of the aromatic hydrocarbons include toluene, xylene, anisole, and limonene. As a fluorene, a dimethyl sulfene is mentioned suitably.

From the viewpoint of improving the properties of the coating surface, a form in which two or more solvents are mixed is also preferable. Among them, selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, Methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethylsulfinium, ethylcarbitol acetate, butylcarbitol ethyl A mixed solution composed of two or more of an acid ester, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable. It is particularly preferable to use dimethyl sulfene and γ-butyrolactone together.

When the resin composition has a solvent, from the viewpoint of coating properties, it is preferable to set the content of the solvent to a total solid content concentration of the resin composition of 5 to 80% by mass, and more preferably 5 to 70% by mass. 10 to 60% by mass is particularly good. The solvent content may be adjusted by the desired thickness and coating method. For example, if the coating method is a spin coating method or a slit coating method, the content of the solvent having a solid content concentration in the above range is preferred. In the case of the spray coating method, the amount is preferably 0.1 to 50% by mass, and more preferably 1.0 to 25% by mass. By adjusting the amount of the solvent by the coating method, a resin composition layer having a desired thickness can be uniformly formed. The solvent may be only one kind, or two or more kinds. When there are two or more solvents, the total is preferably in the above range. From the viewpoint of film strength, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, and N, N-dimethylformamide The content of amidine is preferably less than 5% by mass, more preferably less than 1% by mass, even more preferably less than 0.5% by mass, and even more preferably less than 0.1% by mass.

<<< Sensitizing dye> The resin composition in this invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation and becomes an electronically excited state. The sensitized dye in an electronically excited state is brought into contact with a thermal alkali generator, a photobase generator, a thermal radical polymerization initiator, a photopolymerization initiator, and the like to generate effects such as electron transfer, energy transfer, and heat generation. Thereby, the thermal base generator, the photobase generator, the thermal radical polymerization initiator, and the photopolymerization initiator undergo chemical changes to decompose, and generate radicals, acids, or bases. For details of the sensitizing dye, refer to the descriptions in paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, and incorporate the contents into this specification. When the resin composition contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and 0.5 to 10% by mass relative to the total solid content of the resin composition. Better. The sensitizing dye may be used singly or in combination of two or more kinds.

<< chain transfer agent >> The resin composition in the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by The Society of Polymer Science, Japan, 2005) pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in a molecule is used. These can generate free radicals by supplying hydrogen to low-active radical species, or can generate free radicals by deprotonation after oxidation. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles) can be preferably used. Class, etc.). When the resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and more preferably 100 parts by mass relative to the total solid content of the resin composition. 1 to 5 parts by mass. The chain transfer agent may be only one kind, or two or more kinds. When there are two or more kinds of chain transfer agents, it is preferable that the total is in the above range.

<<<Surfactant> From the viewpoint of improving the coating property, various surfactants may be added to the resin composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The following surfactants are also preferred. [Chemical Formula 29]

When the resin composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass relative to the total solid content of the resin composition, and more preferably 0.005 to 1.0% by mass. The surfactant may be only one kind, or two or more kinds. When two or more kinds of surfactants are contained, the total thereof is preferably in the above range.

<< Higher Fatty Acid Derivatives> In order to prevent polymerization from being hindered by oxygen, a higher fatty acid derivative such as behenic acid or ammonium behenate can be added to the resin composition of the present invention after coating. Localized on the surface of the composition during drying. When the resin composition has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the resin composition. The higher fatty acid derivative may be only one type, or two or more types. When there are two or more types of higher fatty acid derivatives, the total is preferably in the above range.

<< Other additives >> As long as the effect of the present invention is not impaired, the resin composition in the present invention can be blended with various additives as required, for example, inorganic particles, hardeners, hardening catalysts, fillers, and antioxidants. , UV absorber, anti-agglomerating agent, etc. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the resin composition.

<<< Restrictions on Other Contained Substances >> From the viewpoint of the properties of the coated surface, the moisture content of the resin composition in the present invention is preferably less than 5 mass%, and less than 1 mass% is more preferably, less than 0.6. The mass% is particularly good.

From the viewpoint of insulation, the metal content of the resin composition in the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and less than 0.5 mass ppm. Extraordinary. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When a plurality of metals are included, the total of these metals is preferably in the above range. In addition, as a method for reducing the metal impurities inadvertently contained in the resin composition, a raw material having a small metal content can be selected as a raw material constituting the resin composition, and the raw material constituting the composition of the present invention is filtered with a filter, and Polytetrafluoroethylene and other methods are used to line the inside of the device and perform distillation under conditions that minimize contamination.

From the viewpoint of wiring corrosion, the resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and particularly preferably less than 200 mass ppm. Among them, those present in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of a chlorine atom and a bromine atom, or a chloride ion and a bromide ion are in the above-mentioned ranges, respectively.

<Preparation of resin composition> A resin composition can be prepared by mixing each said component. The mixing method is not particularly limited, and can be performed by a conventionally known method. In addition, for the purpose of removing foreign matters such as garbage and particles in the resin composition, it is preferable to perform filtration using a filter. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be previously cleaned with an organic solvent. In the filtering step of the filter, a plurality of filters can be used in parallel or in series. When multiple filters are used, filters with different pore sizes and / or materials can be used in combination. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be cyclic filtering. In addition, filtration may be performed after pressurization. When filtering is performed after pressurization, the pressure for pressurizing is preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using a filter, impurity removal treatment using an adsorbent can also be performed. It is also possible to combine a filter and an impurity removal treatment using an adsorbent. As the adsorbent, a known adsorbent can be used. Examples include inorganic adsorbents such as silica gel and zeolites, and organic adsorbents such as activated carbon.

<The manufacturing method of a laminated body> Next, the manufacturing method of the laminated body of this invention is demonstrated. The manufacturing method of the laminated body of this invention includes the pattern formation method of this invention mentioned above.

In the method for manufacturing a laminated body of the present invention, a negative photosensitive resin composition layer forming step, an exposure step, a developing step, and a heating step are performed to form a pattern of a resin layer on a support, and then the metal layer forming step and the negative step are sequentially performed The pattern forming step of the photosensitive resin composition layer forming step, the exposure step, the developing step, and the heating step are preferably performed 2 to 7 times alternately, and more preferably 2 to 5 times. Thereby, a laminated body having a multilayer wiring structure in which a resin layer and a metal layer formed of a negative photosensitive resin composition layer are alternately laminated can be manufactured. In addition, in such a multilayer body having a multilayer wiring structure, a pattern having a large thickness difference is often formed. In particular, as the number of laminated resin layers increases, a pattern with a larger thickness difference is often formed. Moreover, the conventional method tends to take time due to a large increase in the number of steps. As the number of laminated resin layers increases, warping also occurs in the support and the like, and there is a tendency that the uniformity of the pattern cannot be maintained in the conventional method. In contrast, according to the present invention, it is possible to pattern a resin layer (negative photosensitive resin composition layer) with good efficiency even in a multilayer body of such a multilayer wiring structure. Therefore, by applying the pellet formation method of the present invention to the production of such a laminated body, the effects of the present invention can be easily and more effectively exerted.

FIG. 3 is a diagram showing an example of a multilayer body having a multilayer wiring structure. In the figure, reference numeral 500 indicates a laminated body, reference numerals 201 to 204 indicate resin layers, and reference numerals 301 to 303 indicate metal layers. In addition, the symbol A in FIG. 2 is the thickness of the thinnest pattern among the patterns with different thicknesses formed simultaneously by the pattern forming method of the present invention, and the symbol B is the thickest pattern among the patterns with different thicknesses formed at the same time. thickness of.

The laminated body shown in FIG. 3 is demonstrated. A desired pattern is formed in the resin layer 201. The pattern is formed by negative development. A metal layer 301 is formed on the surface of the resin layer 201. The metal layer 301 is formed so as to cover a part of the surface of the groove 401 formed in the resin layer 201. A resin layer 202 is formed on the metal layer 301. A desired pattern is formed in the resin layer 202 and a part of the metal layer 301 is exposed on the resin layer 202. The pattern is formed by negative development. A metal layer 302 is formed on the surface of the resin layer 202. The metal layer 302 is formed so as to cover a part of the surface of the groove 402 formed in the resin layer 202, and is electrically connected to the metal layer 301 exposed to the resin layer 202. A resin layer 203 is formed on the metal layer 302. A desired pattern is formed in the resin layer 203, and a part of the metal layer 302 is exposed on the resin layer 203. The pattern is formed by negative development. A metal layer 303 is formed on the surface of the resin layer 203. The metal layer 303 is formed so as to cover a part of the surface of the groove 403 formed in the resin layer 203 and is electrically connected to the metal layer 302 exposed to the resin layer 203. A resin layer 204 is formed on the metal layer 303. A desired pattern is formed in the resin layer 204, and a part of the metal layer 303 is exposed on the resin layer 204. A part of the metal layer 302 is also exposed in the resin layer 204 in FIG. 3. The laminated body functions as an insulating film of the resin layers 201 to 204, and the metal layers 301 to 303 function as wiring layers. Such a laminated body can be preferably used as a redistribution layer in an electronic device.

<The manufacturing method of an electronic device> Next, the manufacturing method of the electronic device of this invention is demonstrated. A method of manufacturing an electronic device according to the present invention includes the pattern forming method of the present invention described above. An embodiment of an electronic device obtained by applying the pattern forming method of the present invention will be described with reference to drawings. The electronic device 100 shown in FIG. 4 is a so-called three-dimensional mounting device, and a multilayer body 101 in which a plurality of semiconductor elements (semiconductor wafers) 101 a to 101 d are stacked is arranged on a wiring substrate 120. In addition, in this embodiment, the case where the number of stacked layers of a semiconductor element (semiconductor wafer) is mainly four is described, but the number of stacked layers of a semiconductor element (semiconductor wafer) is not particularly limited, and for example, two layers, eight layers, 16 floors, 32 floors, etc. It can be tied to one floor.

Each of the plurality of semiconductor elements 101a to 101d includes a semiconductor wafer such as a silicon substrate. The uppermost semiconductor element 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof. The semiconductor elements 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) integrally provided on the through electrodes are provided on both surfaces of each semiconductor element.

The laminated body 101 has a structure of flip-chip bonding a semiconductor element 101a without a through electrode and semiconductor elements 101b to 101d with a through electrode 102b to 102d. That is, the electrode pad of the semiconductor element 101a without a through electrode and the connection pad on the semiconductor element 101a side of the semiconductor element 101b with a through electrode 102b adjacent thereto are connected by a metal bump 103a such as a solder bump. The connection pad on the other side of the semiconductor element 101b having the through electrode 102b and the connection pad on the semiconductor element 101b side of the semiconductor element 101c having the through electrode 102c adjacent to the connection pad are formed by a metal bump 103b such as a solder bump. connection. Similarly, the connection pads on the other side of the semiconductor element 101c having the through electrode 102c and the connection pads on the semiconductor element 101c side of the semiconductor element 101d having the through electrode 102d adjacent thereto are connected by metal bumps such as solder bumps. 103c and connected.

An underfill layer 110 is formed in a gap between each of the semiconductor elements 101a to 101d, and each of the semiconductor elements 101a to 101d is laminated via the underfill layer 110.

The laminated body 101 is laminated on the wiring substrate 120. As the wiring substrate 120, for example, a plurality of layers of wiring substrates using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a base material are used. Examples of the wiring substrate 120 to which the resin substrate is applied include a plurality of copper-clad laminated boards (multilayer printed wiring boards) and the like.

A surface electrode 120 a is provided on one surface of the wiring substrate 120. An insulating layer 115 on which the redistribution layer 105 is formed is arranged between the wiring substrate 120 and the multilayer body 101, and the wiring substrate 120 and the multilayer body 101 are electrically connected via the redistribution layer 105. The insulating layer 115 is formed using the pattern forming method of the present invention. The insulating layer 115 may have a multilayer wiring structure as shown in FIG. 3. One end of the redistribution layer 105 is connected to an electrode pad formed on a surface of the redistribution layer 105 side of the semiconductor element 101d via a metal bump 103d such as a solder bump. The other end of the redistribution layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump. Further, an underfill layer 110a is formed between the insulating layer 115 and the laminated body 101. An underfill layer 110b is formed between the insulating layer 115 and the wiring substrate 120. [Example]

Hereinafter, the present invention will be further specifically described by examples. The present invention is not limited to the following examples without departing from the scope of the present invention. In addition, as long as there is no particular limitation, "%" and "part" are quality standards. NMR is short for nuclear magnetic resonance.

(Synthesis Example 1) [Polyimide precursor derived from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and benzyl alcohol (P-1: Polymer without radical polymerizable group Synthesis of hydrazone imide precursor)] 14.06 g (64.5 mmol) of pyromellitic dianhydride (drying at 140 ° C for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol were suspended in 50 ml of N-methylpyrrolidone and dried by molecular sieve. The suspension was heated at 100 ° C for 3 hours. After starting heating and after a few minutes, a clear solution was obtained. The reaction mixture was cooled to room temperature, and 21.43 g (270.9 mmol) of pyridine and 90 ml of N-methylpyrrolidone were added. Next, the reaction mixture was cooled to -10 ° C, and while maintaining the temperature at -10 ± 4 ° C, 16.12 g (135.5 mmol) of SOCl _{2 was} added over 10 minutes. The viscosity increased during the addition of SOCl ₂ . After dilution with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, the reaction mixture was added dropwise with 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether in 100 ml of N-methylpyrrolidone at 20 to 23 ° C over 20 minutes. The resulting solution. Then, the reaction mixture was stirred at room temperature for 1 ton. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor was collected by filtration, poured into 4 liters of water again, and stirred for 30 minutes, and then filtered again. Then, the polyimide precursor was dried at 45 ° C. for 3 days under reduced pressure to obtain a polyimide precursor (P-1) containing a repeating unit represented by the following formula. [Chemical Formula 30]

(Synthesis Example 2) [Polyimide precursor derived from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate (P-2: radical-containing Synthesis of polymerizable polyfluorene imide precursor)] 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diethylene glycol dimethyl ether (diethylene glycol dimethyl ether) were mixed and the temperature was at 60 ° C. After stirring for 18 hours, a diester of pyromellitic acid and 2-hydroxyethyl methacrylate was produced. Next, the obtained diester was chlorinated with SOCl _{2 and} then converted to a polyfluorene imine precursor by 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1. 1 In the same manner, a polyfluorene imide precursor (P-2) containing a repeating unit represented by the following formula was obtained. [Chemical Formula 31]

(Synthesis Example 3) [Polyimide precursor derived from 4,4'-oxybisphthalic anhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate (P -3: Synthesis of a polyimide precursor having a radical polymerizable group)] 20.0 g (64.5 mmol) of 4,4'-oxybisphthalic anhydride (dried at 140 ° C for 12 Hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diethylene glycol dimethyl ether, and mixed at 60 ° C It was stirred at a temperature of 18 hours for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with SOCl _{2 and} then converted to a polyfluorene imine precursor by 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1. 1 In the same manner, a polyfluorene imide precursor (P-3) containing a repeating unit represented by the following formula was obtained. [Chemical Formula 32]

(Synthesis Example 4) [Polyimide precursor derived from 4,4'-oxydiphthalic anhydride and 4,4'-oxydiphenylamine (P-4: polyimide having a carboxyl group Synthesis of precursor)] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C for 12 hours) was dissolved in 180 ml of NMP (N-methyl- 2-pyrrolidone), 21.43 g (270.9 mmol) of pyridine was added, and the reaction solution was cooled to -10 ° C, while maintaining the temperature at -10 ± 4 ° C, 11.08 g (58.7 mmol) A solution obtained by dissolving 4,4'-oxydiphenylamine in 100 ml of NMP was added dropwise over 30 minutes, and then the reaction mixture was stirred at room temperature for 1 ton. Next, 5 liters of water was added to precipitate the polyimide precursor, and the water-polyimide precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor was filtered out, put into 4 liters of water again and stirred for 30 minutes, and filtered again. Next, the obtained polyimide precursor was dried under reduced pressure and dried at 45 ° C for 3 days to obtain a polyimide precursor (P-4) containing a repeating unit represented by the following formula. [Chemical Formula 33]

(Synthesis Example 5) [Synthesis of acrylic polymer (P-6)] 27.0 g (153.2 mmol) of benzyl methacrylate and 20 g (157.3 mmol) of N-isopropylmethacryl Amidine, 39 g (309.2 mmol) of allyl methacrylate, 13 g (151.0 mmol) of methacrylic acid, polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) 3.55 g (15.4 mmol) and 300 g of 3-methoxy-2-propanol were mixed. In a nitrogen environment, the mixed solution was added dropwise to 300 g of 3-methoxy-2-propanol heated to 75 ° C over 2 hours. After completion of the dropwise addition, the mixture was further stirred at 75 ° C. for 2 hours under a nitrogen atmosphere. After completion of the reaction, the polymer was poured into 5 liters of water to precipitate a polymer, and the mixture was stirred at 5000 rpm for 15 minutes. The acrylic resin was removed by filtration, and it was again poured into 4 liters of water and stirred for 30 minutes to perform filtration and removal again. Then, the obtained acrylic resin was dried at 45 ° C. for 3 days under reduced pressure to obtain an acrylic polymer (P-6) represented by the following formula. [Chemical Formula 34]

<Preparation of negative-type photosensitive resin composition> The components described below were mixed, and the coating liquid of the photosensitive resin composition was prepared as a uniform solution. (Composition) Resin: parts by mass of the radical polymerizable compound described in the following table: parts by mass of the photo radical polymerization initiator described in the following table: parts by mass of the silane coupling agent described in the following table: The parts by mass of the rust preventive agent described in the following table: the parts by mass of the polymerization inhibitor described in the following table: the parts by mass of the alkali generator described in the following table: the parts by mass of the solvent 1 in the following table (Dimethylmethylene): 100 parts by mass of solvent 2 (γ-butyrolactone): 25 parts by mass

<Evaluation of the resolution of a negative photosensitive composition> A coating film was formed by coating a negative photosensitive resin composition on a Si substrate. Next, a heat treatment was performed for 240 seconds using a 100 ° C. hot plate to form a negative photosensitive resin composition layer having a film thickness of 15 μm. Next, the negative photosensitive resin composition layer was irradiated with a stepper exposure device FPA-3000i5 + (manufactured by Canon Inc.) through a pattern mask having a 15 μm square Bayer and changing the exposure amount at 100 mJ / cm ² to irradiate 100 to 1000 mJ / cm ² of i-rays (light having a wavelength of 365 nm), and then the Si substrate on which the negative-type photosensitive resin composition layer after exposure was formed was placed in a rotary / spray developing machine (DW-30 type; Chemitronics Co., Ltd.) was developed on a horizontal rotary table using cyclopentanone at 23 ° C. for 60 seconds to remove unexposed portions, thereby forming a pattern. The resolution of the negative photosensitive composition was evaluated according to the following criteria. In addition, when the exposed width of the base substrate is 15 μm ± 3 μm, a pattern (15 μm square pattern) with a line width of 15 μm can be analyzed. A: The difference between the maximum value and the minimum value of the exposure amount capable of analyzing a pattern having a thickness of 15 μm and a line width of 15 μm is 900 mJ / cm ² or more. B: The difference between the maximum value and the minimum value of the exposure amount capable of analyzing a pattern having a thickness of 15 μm and a line width of 15 μm is 600 mJ / cm ² or more and less than 900 mJ / cm ² . C: The difference between the maximum value and the minimum value of the exposure pattern capable of analyzing a pattern having a thickness of 15 μm and a line width of 15 μm is less than 600 mJ / cm ² .

[TABLE 6]

The abbreviations listed in the table are as follows. (Resin) P-1 to P-4: Polyfluorene imide precursors (P-1) to (P-4) synthesized in Synthesis Examples 1 to 4 P-5: Matrimid 5218 (Huntsman Corporation, closed-loop polymerization) Pyriminium) P-6: Acrylic polymer (P-6) synthesized in Synthesis Example 5 P-7: Polymethylmethacrylate (Mw = 15000, manufactured by Sigma-Aldrich Co. LLC.)

(Radical Polymerizable Compound) B-1: SR209 (manufactured by Sartomer company, tetraethylene glycol diacrylate) B-2: NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co, Ltd., ethoxylated isocyanate Uric acid triacrylate) B-3: A-TMMT (manufactured by Shin-Nakamura Chemical Co, Ltd., pentaerythritol tetraacrylate) B-4: A-DPH (manufactured by Shin-Nakamura Chemical Co, Ltd., dipentaerythritol six Acrylate)

(Photo radical polymerization initiator) C-1: IRGACURE OXE 01 (manufactured by BASF, oxime compound) C-2: IRGACURE OXE 02 (manufactured by BASF, oxime compound) C-3: IRGACURE-784 (manufactured by BASF, Metallocene compound) C-4: ADEKA ARKLS NCI-831 (made by ADEKA CORPORATION, oxime compound)

(Silane coupling agent) D-1: KBM-602 (silane compound having an amine group manufactured by Shin-Etsu Chemical Co., Ltd.) D-2: 2-((3- (triethoxysilyl) Propyl) aminomethylamido) benzoic acid (silane compound with carboxyl group produced by Aquila Pharmatech LLC) D-3: triethoxysilylpropylmaleic acid (manufactured by Gelest, Inc. and carboxyl group) Silane compounds)

(Antirust agent) E-1: KEMITEC BT-C (made by CHEMIPRO KASEI KAISHA LTD, 1,2,3-benzotriazole) E-2: 1HT (made by TOYOBO CO., LTD., 1H-tetrazole) E-3: P5T (manufactured by TOYOBO CO., LTD., 5-phenyl-1H-tetrazole)

(Polymerization inhibitor) F-1: 4-methoxyphenol F-2: p-benzoquinone F-3: 1-nitroso-2-naphthol

(Alkali generator) A-1, A-21, A-40: Compounds of the following structure (thermal alkali generator) A-43: WPBG-266 (manufactured by Wako Pure Chemical Industries, Ltd., photo-alkali generator). A compound that generates a base by being decomposed by heating.) [Chemical Formula 35]

<Pattern formation method> A negative photosensitive resin composition is coated on a Si substrate (t1 to t8 = 2 μm, t9 = 0.5 μm, t10 = 0.5 μm, t11 = 1 μm) having a step difference as shown in FIG. The film thickness T1 of the cloth film after drying is set to 20 μm at the thickest part. The coating speed is adjusted to form a coating film, and a 100 ° C heating plate is used for 240 seconds of heat treatment to form a negative photosensitive resin. Composition layer. For the negative photosensitive resin composition layer, a stepper exposure device FPA-3000i5 + (manufactured by Canon Inc.) was used to irradiate 100 to 1000 mJ / with a pattern mask having a 15 μm square Bayer and changing the exposure amount by 100 mJ / cm ² cm ² of i-rays (light at a wavelength of 365 nm). Next, the Si substrate on which the negative photosensitive resin composition layer after exposure was formed was placed on a horizontal rotary table of a rotary / spray developing machine (DW-30 type; manufactured by Chemitronics Co., Ltd.) and a ring was used. The pentanone was developed at 23 ° C. for 60 seconds to remove unexposed portions. Next, a heat treatment was performed at 230 ° C. for 180 minutes in a nitrogen oven to form a pattern on each step of the Si substrate. The thickness of the pattern formed in FIG. 5 is 2 μm, 3 μm, 3.5 μm, 4 μm, 6 μm, 8 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm.

<Evaluation of Resolution> The resolution was evaluated according to the following criteria. When the exposed width of the base substrate after development is 15 μm ± 3 μm, a pattern (15 μm square pattern) capable of analyzing a line width of 15 μm is used. A: A pattern having a line width of 15 μm can be formed in a range of a thickness of 2 to 20 μm. B: A pattern having a line width of 15 μm can be formed in a range of 2 to 16 μm in thickness, but a pattern having a line width of 15 μm cannot be formed in a portion having a thickness of more than 16 μm. C: A pattern having a line width of 15 μm can be formed in a range of 2 to 12 μm in thickness, but a pattern having a line width of 15 μm cannot be formed in a portion having a thickness of more than 12 μm. D: Does not meet any of the above A to C. A pattern with a line width of 15 μm could not be formed in any of the thicknesses of 2 to 20 μm.

[TABLE 7]

As shown in the above table, the examples can form patterns with different thicknesses with a wide exposure amount and good resolution.

10‧‧‧ resin layer

11‧‧‧ negative photosensitive resin composition layer

20‧‧‧ support

50‧‧‧Mask

100‧‧‧ electronic device

101a ～ 101d‧‧‧Semiconductor element

101‧‧‧Laminated body

102b ～ 102d‧‧‧through electrode

103a ～ 103e‧‧‧ metal bump

105‧‧‧ redistribution layer

110, 110a, 110b‧‧‧ Underfill

115‧‧‧ Insulation

120‧‧‧ wiring board

120a‧‧‧ surface electrode

201 ～ 204‧‧‧Resin layer

301 ～ 303‧‧‧metal layer

401 ～ 403‧‧‧slot

500‧‧‧layer

A1, B1, C1, A, B‧‧‧ pattern thickness

t1 ～ t11‧‧‧step difference

T1‧‧‧film thickness

FIG. 1 is a schematic diagram illustrating patterns having different thicknesses. FIG. 2 is a diagram showing a step of forming a pattern shown in FIG. 1. FIG. Fig. 3 is a schematic diagram showing the structure of an embodiment of the laminated body. FIG. 4 is a schematic diagram showing a configuration of an embodiment of an electronic device. FIG. 5 is a view showing a state in which a negative photosensitive resin composition is applied to a Si substrate having a step difference.

Claims (12)

A pattern forming method using a negative photosensitive resin composition containing a resin and a photopolymerization initiator to form a negative photosensitive resin composition layer on a support, and exposing the negative photosensitive resin composition layer and Two or more patterns having different thicknesses are formed simultaneously during development. The thickness of the thickest pattern among the patterns having different thicknesses formed at the same time is 1.5 to 10 times the thickness of the thinnest pattern. As the object, a negative photosensitive resin composition capable of analyzing a maximum exposure value and a minimum exposure value of a pattern having a thickness of 15 μm and a line width of 15 μm or less is 600 mJ / cm ² or more. The pattern forming method according to item 1 of the scope of the patent application, wherein the negative photosensitive resin composition is laminated on the support at least 2 layers, and the negative photosensitive resin composition layer is laminated on the support. Exposure and development are performed simultaneously to form two or more patterns having different thicknesses. The pattern forming method according to item 1 or 2 of the scope of the patent application, wherein the thickness of the thickest pattern among the patterns having different thicknesses formed at the same time is 1.75 to 8 times the thickness of the thinnest pattern. The pattern forming method according to item 1 or 2 of the scope of the patent application, wherein the thickness of the thickest pattern among the patterns having different thicknesses formed at the same time is 2 to 6 times the thickness of the thinnest pattern. The pattern forming method according to item 1 or 2 of the scope of patent application, wherein the difference between the maximum value and the minimum value of the exposure amount capable of analyzing a pattern having a thickness of 15 μm and a line width of 15 μm or less is used as the negative photosensitive resin composition. 900 mJ / cm ² or more of a negative photosensitive resin composition. The pattern forming method according to item 1 or 2 of the scope of the patent application, wherein the aforementioned resin-based polyimide precursor is used. The pattern forming method as described in item 6 of the scope of patent application, wherein the aforementioned polyimide precursor is represented by the following formula (1), [Chemical Formula 1] In formula (1), A ²¹ and A ²² each independently represent an oxygen atom or -NH-, R ²¹ represents a divalent organic group, R ²² represents a tetravalent organic group, and R ²³ and R ²⁴ each independently represent a hydrogen atom or Monovalent organic group. The pattern forming method according to item 7 of the scope of patent application, wherein at least one of R ²³ and R ²⁴ in the aforementioned formula (1) includes a radical polymerizable group. The pattern forming method according to item 7 of the scope of patent application, wherein R ²² in the aforementioned formula (1) contains a tetravalent group of an aromatic ring. The pattern forming method described in item 1 or 2 of the patent application scope further includes a step of forming a metal layer. A method for manufacturing a laminated body, which includes the pattern forming method according to any one of claims 1 to 10 of a patent application scope. A method for manufacturing an electronic device includes the pattern forming method described in any one of claims 1 to 10 of the scope of patent application.