JP6745344B2 - Pattern forming method, laminated body manufacturing method, and electronic device manufacturing method - Google Patents

Description

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

Polyimide has excellent heat resistance and insulating properties, and is therefore used in insulating layers of electronic devices. In addition, since polyimide has low solubility in solvents, it is applied to a support etc. in the state of the precursor (polyimide precursor) before the cyclization reaction, and then heated to cyclize the polyimide precursor to form a cured film. Things are also being done.

For example, Patent Documents 1 and 2 describe forming a pattern using a negative photosensitive resin composition containing a polyimide precursor and a photopolymerization initiator.

JP, 2011-191749, A JP, 2014-201695, A

In forming a pattern using a negative photosensitive resin composition, in recent years, a pattern is formed on a negative photosensitive resin composition layer formed on a support having a step, or a negative photosensitive resin composition is formed. Two or more types of patterns may be formed by laminating a plurality of resin composition layers. In such a case, two or more types of patterns having different thicknesses will be formed. When forming two or more types of patterns having different thicknesses, a method is used in which the mask and the exposure amount are changed for each pattern thickness. However, in this case, it is necessary to perform the exposure step a plurality of times, which increases the number of steps. Further, as the thickness difference between the patterns becomes large, it tends to be difficult to form a desired pattern shape.

It should be noted that Patent Documents 1 and 2 do not describe or suggest formation of patterns having different thicknesses.

Therefore, 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 types of patterns having different thicknesses with high resolution with a wide exposure amount. is there.

Based on the above problems, as a result of studies by the inventor, the inventors have found that the above problems can be solved by the following pattern forming method, and have completed the present invention. The present invention provides the following.
<1> A negative photosensitive resin composition layer is formed on a support using a negative photosensitive resin composition containing a resin and a photopolymerization initiator, and the negative photosensitive resin composition layer is exposed and A pattern forming method of performing development to simultaneously form two or more types of patterns having different thicknesses,
Among the patterns having different thicknesses formed at the same time, the thickness of the thickest pattern is 1.5 to 10 times the thickness of the thinnest pattern,
As a negative photosensitive resin composition, a negative photosensitive resin composition in which the difference between the maximum value and the minimum value of the exposure amount capable of resolving a pattern having a thickness of 15 μm and a line width of 15 μm or less is 600 mJ/cm ² or more. A pattern forming method using.
<2> Two or more negative photosensitive resin composition layers are laminated on a support, and two or more negative photosensitive resin composition layers are exposed and developed to have different thicknesses. The pattern forming method according to <1>, wherein at least one kind of pattern is formed at the same time.
<3> The pattern formation according to <1> or <2>, in which the thickness of the thickest pattern is 1.75 to 8 times the thickness of the thinnest pattern among the patterns having different thicknesses formed at the same time. Method.
<4> The pattern forming method according to <1> or <2>, in which the thickness of the thickest pattern is 2 to 6 times the thickness of the thinnest pattern among the patterns having different thicknesses formed at the same time.
<5> As a negative photosensitive resin composition, a negative photosensitive resin in which the difference between the maximum value and the minimum value of the exposure amount capable of resolving a pattern having a thickness of 15 μm and a line width of 15 μm or less is 900 mJ/cm ² or more. The pattern forming method according to any one of <1> to <4>, which uses a composition.
<6> The pattern forming method according to any one of <1> to <5>, in which the resin is a polyimide precursor.
<7> The pattern forming method according to <6>, wherein the polyimide precursor is represented by the following formula (1):
In the 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, R ²³ and R ²⁴ each independently represent a hydrogen atom or a monovalent organic group.
<8> The pattern forming method according to <7>, wherein in the formula (1), at least one of R ²³ and R ²⁴ contains a radically polymerizable group.
<9> The pattern forming method according to <7> or <8>, wherein R ²² in the formula (1) is a tetravalent group containing an aromatic ring.
<10> The pattern forming method according to any one of <1> to <9>, further including a step of forming a metal layer.
<11> A method for manufacturing a laminated body, including the pattern forming method according to any one of <1> to <10>.
<12> A method for manufacturing an electronic device, including the pattern forming method according to any one of <1> to <10>.

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

It is a schematic diagram explaining patterns with different thicknesses. FIG. 3 is a diagram showing a process of forming the pattern shown in FIG. It is a schematic diagram showing the composition of one embodiment of a layered product. It is a schematic diagram showing the composition of one embodiment of an electronic device. It is a figure which shows the state which applied the negative photosensitive resin composition on the Si substrate which has a level|step difference.

The components of the present invention described below may be described based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the description of the group (atomic group) in the present specification, the description without substitution and without substitution includes a group having a substituent as well as a group having no substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, the term “exposure” includes not only exposure using light but also drawing using a particle beam such as an electron beam or an ion beam unless otherwise specified. As the light used for the exposure, generally, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron rays, or radiation is exemplified.
In the present specification, the numerical range represented by “to” means a range including the numerical values before and after “to” as the lower limit value and the upper limit value.
In the present specification, “(meth)acrylate” means both “acrylate” and “methacrylate” or either, and “(meth)allyl” means both “allyl” and “methallyl”, or Represents either, "(meth) acrylic" represents both "acrylic" and "methacryl", or either, "(meth) acryloyl" is both "acryloyl" and "methacryloyl", or Represents either.
In the present specification, the term “step” is included in this term as long as the intended action of the step is achieved not only as an independent step but also when it cannot be clearly distinguished from other steps. ..
In the present specification, the solid content concentration is a mass percentage of other components excluding the solvent with respect to the total mass of the composition. Further, the solid content concentration refers to the concentration at 25° C. unless otherwise specified.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene equivalent values according to gel permeation chromatography (GPC) measurement, unless otherwise specified. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and the columns are guard columns HZ-L, TSKgel Super HZM-M, and TSKgel. It can be determined by using Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). The eluent is THF (tetrahydrofuran) unless otherwise specified. In addition, detection is performed using a UV ray (ultraviolet) wavelength 254 nm detector unless otherwise specified.

<Pattern forming method>
The pattern forming method of the present invention comprises forming a negative photosensitive resin composition layer using a negative photosensitive resin composition containing a resin and a photopolymerization initiator, and exposing the negative photosensitive resin composition layer to light. And a pattern formation method of performing development to simultaneously form two or more types of patterns having different thicknesses. Among the patterns having different thicknesses formed simultaneously, the thickness of the thickest pattern is the thickness of the thinnest pattern. The difference between the maximum value and the minimum value of the exposure amount capable of resolving a pattern having a thickness of 15 μm and a line width of 15 μm or less as a negative photosensitive resin composition is 600 mJ/cm. It is characterized by using a negative photosensitive resin composition of ² or more.

According to the present invention, by using a negative photosensitive resin composition having a difference between the maximum value and the minimum value of the above-mentioned exposure amount of 600 mJ/cm ² or more as a negative photosensitive resin composition, a wide range of exposure can be achieved. Depending on the amount, it is possible to simultaneously form two or more types of patterns having different thicknesses with good resolution. Therefore, it is possible to form patterns having different thicknesses with good resolution with a small number of steps. Further, since the above pattern can be formed with a wide range of exposure dose, a desired pattern can be obtained even if performance variation of the photosensitive composition over time (for example, sensitivity reduction) or variation in the device occurs. Can be expected. In the present invention, forming two or more types of patterns having different thicknesses at the same time means forming two or more types of patterns having different thicknesses by a single exposure and development operation.

In the present invention, the maximum value and the minimum value of the exposure amount capable of resolving a pattern having a thickness of 15 μm and a line width of 15 μm or less are values defined by the following. In pattern resolution, if the exposure amount at the time of exposure is too low, curing of the negative photosensitive resin composition layer does not proceed sufficiently and a desired pattern cannot be resolved. On the other hand, if the exposure amount is too high, the unexposed portion of the peripheral portion of the mask is hardened to cause pattern thickening, and a pattern of a desired size cannot be resolved. The negative photosensitive resin composition is applied to a support and dried to form a negative photosensitive resin composition layer having a thickness of 15 μm, and the exposure amount for the negative photosensitive resin composition layer having a thickness of 15 μm. When exposed to light to form a pattern having a thickness of 15 μm and a line width of 15 μm or less (preferably a line width of 15 μm) by developing and removing the unexposed portion, the exposure amount at the time of exposure is changed and exposed, Of the exposure doses capable of resolving a pattern having a thickness of 15 μm and a line width of 15 μm or less (preferably a line width of 15 μm), the lowest exposure dose value is defined as the minimum exposure dose value, and the highest exposure dose value is defined. Is the maximum value of the exposure amount. For example, although it resolve the pattern at an exposure dose of up to 100 mJ / cm ^2, below the 100 mJ / cm ^2, curing does not proceed sufficiently, and if you can not resolve the above pattern, 100 mJ / cm ² is It is the minimum value of the exposure amount. Further, for example, when the exposure amount is up to 1000 mJ/cm ² , the above pattern can be resolved, but when it exceeds 1000 mJ/cm ² , pattern thickening occurs and the above pattern cannot be resolved, 1000 mJ/cm ² Is the maximum value of the exposure amount. As light (radiation) used for exposure, radiation such as visible light, ultraviolet light, far ultraviolet light, charged particle beam, and X-ray can be appropriately selected and used, but the wavelength is in the range of 190 to 450 nm. Certain light (radiation) is preferred. For example, it is preferable to perform pattern exposure using a light exposure device such as a stepper through a mask having a Bayer pattern of 1 μm to 1 μm in every 1 μm. The light (radiation) that can be used in the exposure is preferably ultraviolet rays such as g-line and i-line, and more preferably i-line.
In addition, in this invention, the line width of a pattern is the line width of the development removal part (negative pattern) of a negative photosensitive resin composition layer. Further, in the present invention, it is assumed that a pattern having a desired size can be resolved when the exposed width of the base is 0.8 to 1.2 times the mask size. For example, when a pattern is formed using a mask having a line width of 15 μm, it is assumed that a pattern having a line width of 15 μm can be resolved when the exposed width of the base 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 above-mentioned exposure amount is 600 mJ/cm ² or more, and preferably 700 mJ/cm ² or more, more preferably 800 mJ / cm ² or more, more preferably 900 mJ / cm ² or more. The upper limit is not particularly limited, since they can reduce the time required for each step, is preferably 1800 mJ / cm ² or less, more preferably 1700mJ / cm ² or less, 1600 mJ / cm ² or less Is more preferable. Regarding the negative photosensitive resin composition, at least one selected from the maximum value and the minimum value of the above exposure amount (preferably the minimum value of the above exposure amount) is in the range of 50 to 500 mJ/cm ² (more It is preferably in the range of 100 to 400 mJ/cm ² . It is particularly preferable that both the maximum value and the minimum value of the exposure dose described above are in the range of 10 to 2000 mJ/cm ² (more preferably in the range of 50 to 1800 mJ/cm ² ).

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

Further, in the present invention, the thickness of the thickest pattern and the thickness of the thinnest pattern in the patterns formed at the same time having different thicknesses mean the thickness of the pattern formed by negative development. For example, A1, B1, and C1 in FIG. 1 are pattern thicknesses, B1 in FIG. 1 corresponds to the thickest pattern thickness, and A1 in FIG. 1 corresponds to the thinnest pattern thickness. Reference numeral 10 in FIG. 1 is a resin layer formed using a negative photosensitive resin composition, and reference numeral 20 is a structure such as a support or a metal layer. In the pattern shown in FIG. 1, a negative photosensitive resin composition layer 11 is formed on a support 20 having steps such as irregularities (FIG. 2(A)), and then exposed through a mask 50 having a pattern. (FIG. 2(B)), and then the unexposed portion is developed and removed (FIG. 2(C)) to form a desired pattern.

In the present invention, among the patterns having different thicknesses formed simultaneously, the thickness of the thickest pattern is 1.5 to 10 times, preferably 1.75 to 8 times the thickness of the thinnest pattern. , 2 to 6 times is more preferable. In the present invention, the pattern thickness means the pattern thickness 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 further preferably 50 μm or less. The lower limit is preferably 0.1 μm or more, more preferably 1 μm or more, and further preferably 5 μm or more.
In the present invention, the thickness of the thickest pattern among the patterns formed at the same time and having different thicknesses is preferably 0.1 to 100 μm. The upper limit is preferably 90 μm or less, more preferably 75 μm or less, and further preferably 50 μm or less. The lower limit is preferably 0.5 μm or more, more preferably 1 μm or more, still 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, still more preferably 3 μm or more.

In the pattern forming method of the present invention, two or more layers of the above-mentioned negative photosensitive resin composition layer are laminated on a support, and the negative photosensitive resin composition layer laminated by two or more layers is exposed and developed. Therefore, it is preferable to simultaneously form two or more types of patterns having different thicknesses. When two or more negative type photosensitive resin composition layers are laminated, the thickness of the negative type photosensitive resin composition layer may vary due to unevenness of the support as the base. Therefore, a pattern having a larger difference in thickness may be formed, but according to the present invention, even in such a case, two or more types of patterns having 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 comprises 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 Physical layer forming step). In the present invention, as the negative photosensitive resin composition, a negative photosensitive resin composition in which the difference between the maximum value and the minimum value of the exposure amount is 600 mJ/cm ² or more is used. Details of the negative photosensitive resin composition will be described later.

The type of support can be appropriately determined according to the application. For example, an inorganic substrate, a resin substrate, a resin composite material substrate, or the like can be given. Examples of the inorganic substrate include a glass substrate, a quartz substrate, a silicon substrate, a silicon nitride (silicon nitride) substrate, and a composite substrate obtained by depositing molybdenum, titanium, aluminum, copper, or the like on such a substrate. The resin substrate, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, Polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, Substrates made of synthetic resins such as aromatic ethers, maleimides, olefins, celluloses and episulfide compounds can be mentioned. These substrates are rarely used as they are, and usually, a multilayer laminated structure such as a thin film transistor (TFT) element is formed depending on the form of the final product. Incidentally, in the case of further forming a negative photosensitive resin composition layer on the surface of the negative photosensitive resin composition layer having a metal layer or the like, the metal layer or the negative photosensitive resin composition layer serves as a support. Become.

As a method for applying the negative photosensitive resin composition to the support, coating is preferable. Specific application methods include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spin coating method, a slit scan method, and an inkjet method. It From the viewpoint of the uniformity of the thickness of the negative photosensitive resin composition layer, the spin coating method is more preferable. In the case of the spin coating method, for example, 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 such that the film thickness after heating is 0.05 to 100 μm, and more preferably 1 to 50 μm. The thickness of the negative photosensitive resin composition layer formed does not necessarily have to be uniform. For example, as shown in FIG. 1, when a negative photosensitive resin composition layer is formed on an uneven surface, the negative photosensitive resin composition layers may have different thicknesses.

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, further preferably 90 to 110°C. The drying time is preferably 30 seconds to 20 minutes, more preferably 1 to 10 minutes, still 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 the negative photosensitive resin composition layer. Specifically, an exposure step of exposing the negative photosensitive resin composition layer in a pattern, and a developing step of developing and removing an unexposed portion of the exposed resin composition layer to form a pattern. Including steps. Then, in the present invention, the negative photosensitive resin composition layer is exposed and developed to simultaneously form two or more types of patterns having different thicknesses. In order to form two or more types of patterns having different thicknesses at the same time, a negative photosensitive resin composition layer is formed on a support having steps such as unevenness, and the negative photosensitive resin composition layer having different thicknesses is formed. On the other hand, there is a method of simultaneously exposing and developing to form a pattern. Examples of the support having steps such as unevenness include a support having a structure such as a metal layer formed on the surface thereof.

In the exposure step, the exposure to the negative photosensitive resin composition layer is preferably performed at 50 to 10000 mJ/cm ^{2 in} terms of exposure energy at a wavelength of 365 nm, and preferably at 100 to 8000 mJ/cm ² . Is more preferable. The exposure wavelength can be appropriately set in the range of 190 to 1000 nm, and preferably 240 to 550 nm.

In the developing step, the negative photosensitive resin composition layer is preferably developed using a developer. The developer can be used without particular limitation. Solvents are preferred. Examples of the solvent used in the developing solution include organic solvents such as esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides. For these details, the solvents described in the section of the resin composition described later can be mentioned. Among them, 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, Dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether and propylene glycol methyl ether acetate are preferable, and cyclopentanone and γ-butyrolactone are more preferable.

The developing time is preferably 10 seconds to 5 minutes. The temperature at the time of development is not particularly limited, but may be 20 to 40°C. After the treatment with the developing solution, rinsing may be further performed. Rinsing is preferably performed in a solvent different from the developing solution. For example, rinsing can be performed using the solvent contained in the resin composition. The rinse time is preferably 5 seconds to 1 minute.

The pattern forming method of the present invention preferably includes a heating step of heating the pattern obtained by the developing step. In the heating step, the cyclization reaction of the polyimide precursor proceeds. When the negative photosensitive resin composition contains a radical polymerizable component such as a radical polymerizable compound, the unreacted radical polymerizable component also cures. As a result, a pattern having excellent heat resistance can be formed.

The maximum heating temperature (maximum temperature during heating) in the heating step is preferably 100 to 500°C, more preferably 140 to 400°C, and further preferably 160 to 350°C.
The heating is preferably performed at a temperature rising rate of 1 to 12°C/minute from a temperature of 20 to 150°C to the maximum heating temperature, more preferably 2 to 10°C/minute, and further preferably 3 to 10°C/minute. By setting the heating rate to 1° C./minute or more, it is possible to prevent excessive volatilization of the amine while ensuring high productivity, and to obtain it by setting the heating rate to 12° C./minute or less. The residual stress of the film can be relaxed.
The temperature at the start of heating is preferably 20 to 150°C, more preferably 20°C to 130°C, and further preferably 25°C 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 onto a support and then dried, the temperature after the drying is the heating start temperature. In the heating step, for example, it is preferable to gradually raise the temperature from 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 is preferably performed for 10 to 360 minutes, more preferably 20 to 300 minutes, and particularly preferably 30 to 240 minutes.

The heating in the heating step may be performed stepwise. As an example, the temperature is raised from 25°C to 180°C at 3°C/minute, and kept at 180°C for 60 minutes, from 180°C to 200°C at 2°C/minute, and at 200°C for 120 minutes , And the like.

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

After finishing the heating process, it is preferable to cool. 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 existing metal species can be used. For example, copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are mentioned, copper and aluminum are preferable, and copper is more preferable. The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining these can be considered. More specifically, a patterning method that combines sputtering, photolithography and etching, and a patterning method that combines photolithography and electrolytic plating can be mentioned.
The thickness of the metal layer is preferably 0.1 to 50 μm in the thickest portion, more preferably 1 to 10 μm.

In the pattern forming method of the present invention, when the step of forming a metal layer is included, the method further includes a step of surface-activating at least a part of the metal layer and the negative photosensitive resin composition layer (surface activation treatment step). You may stay. The surface activation treatment may be performed on at least a part of the metal layer, or may be performed on at least a part of the negative photosensitive resin composition layer after the developing step (after the heating step when the heating step is further performed). Or at least part of each of the metal layer and the negative photosensitive resin composition layer.
The surface activation treatment is usually performed after forming the metal layer. However, after the development step (after the heating step when the heating step is further performed), the surface activation treatment is performed on the negative photosensitive resin composition layer. Therefore, a metal layer may be formed.
The surface activation treatment is preferably performed on at least a part of the metal layer, and the surface activation treatment is performed on a part or all of the region of the metal layer where the negative photosensitive resin composition layer is formed on the surface. Is preferred. By thus performing the surface activation treatment on the surface of the metal layer, it is possible to improve the adhesiveness with the negative photosensitive resin composition layer provided on the surface.
The surface activation treatment is also preferably performed on a part or the whole of the negative photosensitive resin composition layer. Thus, by performing the surface activation treatment on the surface of the negative photosensitive resin composition layer, the adhesion with the metal layer or the negative photosensitive resin composition layer provided on the surface activated treatment is improved. Can be made
Examples of the surface activation treatment include plasma treatment of various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, CF ₄ /O ₂ , NF ₃ /O. ₂ , SF ₆ , NF ₃ , NF ₃ /O ₂ etching treatment, ultraviolet (UV) ozone surface treatment, dipping in a hydrochloric acid aqueous solution to remove the oxide film, and then a compound having at least one amino group and thiol group It is selected from dipping treatment in an organic surface treatment agent containing it and mechanical surface roughening treatment using a brush, and plasma treatment is preferable, and oxygen plasma treatment using oxygen as a raw material gas is particularly preferable. For corona discharge treatment, the energy is preferably 500~200000J / ^{m 2,} more preferably ^{1000~100000J / m 2, 10000~50000J / m} 2 is most preferred.

In the pattern forming method of the present invention, after the metal layer is formed, the negative photosensitive resin composition layer forming step described above, the exposure step described above, the developing step described above, and the heating step described above are performed again in this order. It is preferable. It is also preferable to further perform the above-mentioned metal layer forming step after the heating step. By doing so, it is possible to form a laminated body in which the resin layers and the metal layers are alternately laminated.

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

<< resin >>
The resin composition in the present invention contains a resin. Examples of the resin include a polyimide precursor, a polybenzoxazole precursor, polyimide, polybenzoxazole, an epoxy resin, and a phenol resin. In the present invention, the resin is preferably a polyimide precursor. The polyimide precursor is preferably a polyimide precursor containing a repeating unit represented by the formula (1).
Formula (1)
In the 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, R ²³ and R ²⁴ each independently represent a hydrogen atom or a monovalent organic group.

A ²¹ and A ²² each independently represent an oxygen atom or —NH—, and an oxygen atom is preferable.

R ²¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a group containing a cyclic aliphatic group and an aryl group, and a linear or branched aliphatic group having 2 to 20 carbon atoms or 6 carbon atoms. To a cyclic aliphatic group having from 20 to 20 carbon atoms, an aryl group having from 6 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and a group consisting of an aryl group having from 6 to 20 carbon atoms is more preferable. The following are mentioned as an example of an aryl group.

In the formula, A is a single bond or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(= O) ₂ — and —NHCO—, and a group selected from a combination thereof are preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, —O—, — C (= O) -, - S -, - SO 2 - , more preferably a group selected _{from, -CH 2 -, - O -} , - S -, - SO 2 -, - C (CF 3 _{) 2 -, - C (CH} 3) 2 - and more preferably a divalent group selected from.

Specific examples of R ²¹ include a diamine residue remaining after the removal of the following amino groups of diamine.
1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1, 2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3 -Aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- and p-phenylenediamine, diaminotoluene, 4,4'- and 3,3'-diaminobiphenyl, 4,4'- and 3,3'-diaminodiphenyl ether, 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenyl sulfone, 4,4'- and 3 ,3'-diaminodiphenyl sulfide, 4,4'- and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diamino Biphenyl, 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-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4′-diaminopara Terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-( 2-Aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3′-dimethyl-4,4′-diaminodiphenylsulfone , 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)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-amino Phenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-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'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- 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)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, diaminobenzoic acid Acid ester, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5- Bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 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]hexafluoropropane, 2,2-bis[4 -(4-Aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4- Amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 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-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine and 4,4'' At least one diamine selected from'-diaminoquaterphenyl.

Further, diamine residues remaining after the removal of the amino groups of diamines (DA-1) to (DA-18) shown below are also mentioned as examples of R ²¹ .

In addition, a diamine residue remaining after removal of the amino group of a diamine having two or more alkylene glycol units in the main chain is also mentioned as an example of R ²¹ . A diamine residue containing two or more of ethylene glycol chain, propylene glycol chain or both in one molecule is preferable, and a diamine residue containing no aromatic ring is more preferable. As an example, 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 product names, manufactured by HUNTSMAN Co., Ltd., 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propane) 2-yl)oxy)propan-2-amine and the like, but 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.

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

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

Formula (1-1)
In formula (1-1), R ¹¹² is a single bond or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—, —SO. _2- and -NHCO-, and a group selected from a combination thereof are preferable, and a single bond or an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-,- CO -, - S- and -SO ₂ -, more preferably a divalent group selected _{from, -CH 2 -, - C (} CF 3) 2 -, - C (CH 3) 2 -, - O -, - CO -, - S- and -SO ₂ - 2 divalent radical selected from the group consisting of is more preferable.

Formula (1-2)

Examples of R ²² include a tetracarboxylic acid residue remaining after the acid anhydride group is removed from the tetracarboxylic dianhydride. Specific examples include the tetracarboxylic acid residue remaining after the acid anhydride group is removed from the following tetracarboxylic dianhydride.
Pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfide tetracarboxylic dianhydride, 3,3 ',4,4'-Diphenylsulfone tetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic acid dianhydride 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetra Carboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic 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-perylenetetracarboxylic 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 alkyl derivatives having 1 to 6 carbon atoms and carbon numbers At least one tetracarboxylic dianhydride selected from the alkoxy derivatives of 1 to 6.

Moreover, the tetracarboxylic acid residue remaining after removing the acid anhydride group from the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below is also mentioned as an example of R ²² .

From the viewpoint of solubility in an alkaline developer, R ²² preferably has an OH group. More specifically, examples of R ²² include tetracarboxylic acid residues remaining after the removal of the anhydride group 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 linear or branched alkyl group, a cyclic alkyl group, a group containing an aromatic group, and a radical polymerizable group. In the present invention, at least one of R ²³ and R ²⁴ is preferably a group containing a radically polymerizable group. According to this aspect, the effect of the present invention tends to be more significantly obtained. Further, the photosensitive resin composition containing this polyimide precursor can be preferably used as a negative photosensitive resin composition. Examples of the radically polymerizable group include groups having an ethylenically unsaturated bond. Specific examples of the radically polymerizable group include a vinyl group, a (meth)allyl group, a group represented by the following formula (III), and the like.

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferable.
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. Examples of suitable R ²⁰¹ include ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene. _{group, -CH 2 CH (OH) CH} 2 - and the like, ethylene group, propylene group, trimethylene _{group, -CH 2 CH (OH) CH} 2 - is more preferable. A combination in which R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group is particularly preferable.

The linear or branched alkyl group preferably has 1 to 30 carbon atoms. Specific examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, octadecyl group, isopropyl group, isobutyl group, Examples thereof include sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group.
The cyclic alkyl group may be either a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group and pinenyl group. Can be mentioned. Of these, a cyclohexyl group is preferable from the viewpoint of compatibility with high sensitivity.
As the aromatic group, a substituted or unsubstituted benzene ring group, naphthalene ring group, pentalene ring group, indene ring group, azulene ring group, heptalene ring group, indacene ring group, perylene ring group, pentacene ring group, acenaphthene ring group , Phenanthrene ring group, anthracene ring group, naphthacene ring group, chrysene 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, indolizine ring group, indole ring group, benzofuran ring group, benzothiophene ring group, isobenzofuran ring group, quinolidine ring group, quinoline ring group, Phthalazine ring group, naphthyridine ring group, quinoxaline ring group, quinoxazoline ring group, isoquinoline ring group, carbazole ring group, phenanthridine ring group, acridine ring group, phenanthroline ring group, thianthrene ring group, chromene ring group, xanthene ring group, Examples thereof include a phenoxathiin ring group, a phenothiazine ring group and a phenazine ring group. A benzene 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 polyimide precursor is an ethylenic It may form a counter salt with a tertiary amine compound having a saturated bond. Examples of such a tertiary amine compound having an ethylenically unsaturated bond include N,N-dimethylaminopropyl methacrylate.

Further, in the case of alkali development, the polyimide precursor preferably has a fluorine atom in the structural unit from the viewpoint of improving the resolution. The fluorine atom imparts water repellency to the surface of the film during alkali development, and can prevent penetration from the surface. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and is preferably 20% by mass or less from the viewpoint of solubility in an alkaline aqueous solution.

The polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving the adhesion to the substrate. Specific examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

Further, in order to improve the storage stability of the resin composition, the main chain end of the polyimide precursor is sealed with a terminal blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound. Preferably. Of these, it is more preferable to use monoamine. Preferred compounds of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene. , 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy- 7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 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-amino Benzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like can be mentioned. To be Two or more of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end capping agents.

The polyimide precursor may be composed of a repeating unit represented by the formula (1) and another repeating unit which is another polyimide precursor.
When the polyimide precursor contains other repeating units, the proportion of the other repeating units in the polyimide precursor is preferably 1 to 60 mol %, more preferably 5 to 50 mol %.

The polyimide precursor in the present invention may have a configuration substantially free of other polyimide precursors other than the polyimide precursor containing the repeating unit represented by the formula (1). The phrase “substantially free from” means, for example, that 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 further preferably 23,000 to 25,000. The polydispersity (Mw/Mn) of the polyimide precursor is not particularly limited, but is preferably 1.0 or more, more preferably 2.5 or more, and further preferably 2.8 or more. preferable. The upper limit of the polydispersity of the polyimide precursor is not particularly limited, but is, for example, preferably 4.5 or less, and may be 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, further preferably 60 to 99% by mass, and 70 to 99% by mass with respect to the total solid content of the resin composition. Is particularly preferable.
The content of the polyimide precursor in the resin composition is preferably 20 to 100% by mass, more preferably 50 to 99% by mass, further preferably 60 to 99% by mass, and 70 to 99, based on the total solid content of the resin composition. Mass% is particularly preferred.
Further, in the present invention, it is also possible to adopt a configuration in which a resin other than the polyimide precursor is substantially not included. The phrase “substantially free from” means, for example, that the content of the resin other than the polyimide precursor contained in the resin composition is 3 mass% or less of the content of the polyimide precursor.

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

In the present invention, a monomer-type radically polymerizable compound (hereinafter, also referred to as a radically polymerizable monomer) is a compound different from a polymer compound. The radical polymerizable monomer is typically a low molecular weight compound, preferably a low molecular weight compound having a molecular weight of 2000 or less, more preferably a low molecular weight compound having a molecular weight of 1500 or less, and a low molecular weight of 900 or less. More preferably, it is a compound. The molecular weight of the radically polymerizable monomer is usually 100 or more.
The oligomer type radically polymerizable compound is typically a polymer having a relatively low molecular weight, and is preferably a polymer in which 10 to 100 radically polymerizable monomers are bonded. As for the molecular weight, the polystyrene-equivalent weight average molecular weight by gel permeation chromatography (GPC) method is preferably 2000 to 20000, more preferably 2000 to 15000, and even more preferably 2000 to 10000.

The number of functional groups of the radically polymerizable compound in the invention means the number of radically polymerizable groups in one molecule. From the viewpoint of resolution, the resin composition preferably contains at least one bifunctional or more radically polymerizable compound containing two or more radically polymerizable groups, and at least one bifunctional to tetrafunctional radically polymerizable compound. It is more preferable to include a seed.

Examples of the radically polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably unsaturated carboxylic acids. Esters of acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional compound. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, thiols, and halogen groups. A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as or tosyloxy group with a monofunctional or polyfunctional alcohol, amine, or thiol is also suitable. Further, as another example, it is possible to use a compound group in which unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is substituted for the unsaturated carboxylic acid. As specific examples, the description in paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification.

As the radically 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, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol. Poly(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane, etc. Compounds obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth)acrylated are described in JP-B-48-41708, JP-B-50-6034, and JP-A-51-37193. Such as urethane (meth)acrylates, polyester acrylates described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490, epoxy resins and (meth)acrylics. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP 2008-292970 A are also suitable.

Examples of the radically polymerizable compound include a group having a fluorene ring and a group having an ethylenically unsaturated bond, which are described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, and the like. It is also possible to use compounds having more than one or cardo resin. Further, as other examples, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, and JP-A-2-25493 are described. The vinyl phosphonic acid-based compound and the like can also be mentioned. Further, the compounds containing a perfluoroalkyl group described in JP-A-61-22048 can also be used. Furthermore, the Japan Adhesive Association magazine, vol. 20, No. 7, those introduced as photopolymerizable monomers and oligomers on pages 300 to 308 (1984) can also be used.

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

In each of the above formulas, n is an integer of 0 to 14 and m is an integer of 0 to 8. The plurality of R and T existing in the molecule may be the same or different.
In each of the above formulas (MO-1) ~ compounds represented by (MO-5), at least one of the plurality of R may, -OC (= O) CH = CH 2, or, -OC (= O) represents a group represented by C(CH ₃ )═CH ₂ .
Specific examples of the compounds represented by the above formulas (MO-1) to (MO-5) include the compounds described in paragraphs 0248 to 0251 of JP2007-269779A.

Further, compounds described in JP-A-10-62986 as formulas (1) and (2) together with specific examples thereof, which are (meth)acrylated after ethylene oxide or propylene oxide is added to a polyfunctional alcohol, It can be used as a radically polymerizable compound. Further, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as the radically polymerizable compound, and the contents thereof are incorporated in the present specification.

Examples of the radically polymerizable compound include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nippon Kayaku (Japanese chemical). Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd., dipentaerythritol penta(meth)acrylate (as a commercial product, KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meta). Acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth)acryloyl groups are bound via ethylene glycol and propylene glycol residues. The structure which has is preferable. These oligomer types can also be used. Pentaerythritol derivatives and/or dipentaerythritol derivatives of the above formula (MO-1) and formula (MO-2) are also preferred examples. Further, SR209 manufactured by Sartomer can also be used.

The radically polymerizable compound may have an acid group such as a carboxyl group, a sulfo group and a phosphoric acid group. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd. The acid value of the radically polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH/g, particularly preferably 5 to 30 mgKOH/g. When the acid value of the above compound is in the above range, the production and handling properties are excellent, and further, the developability is excellent. In addition, radical polymerizability is good.

A compound having a caprolactone structure can also be used as the radically polymerizable compound. The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, for example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, Mention is made of an ε-caprolactone-modified polyfunctional (meth)acrylate obtained by esterifying (meth)acrylic acid and ε-caprolactone with a polyhydric alcohol such as tripentaerythritol, glycerin, diglycerol and trimethylolmelamine. You can Among them, the compound represented by the following formula (C) is preferable.

Formula (C)

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

Formula (D)

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

Formula (E)

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

Such a compound having a caprolactone structure is commercially available, for example, from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m=1 in the above formulas (C) to (E), the formula (D)). The number of groups represented by = 2, compounds in which R ¹ is all hydrogen atoms), DPCA-30 (the same formula, m = 1, the number of groups represented by formula (D) = 3, and R ¹ are all A compound which is a hydrogen atom), DPCA-60 (the same formula, m=1, the number of groups represented by the formula (D)=6, compounds in which all R ¹ are hydrogen atoms), DPCA-120 (in the same formula) m=2, the number of groups represented by the formula (D)=6, compounds in which all R ^{1 s} are hydrogen atoms) and the like.

The radically polymerizable compound is also preferably at least one selected from the group of compounds represented by the following general formula (i) or (ii).

Wherein (i) and Formula (ii), E are each _{independently, - ((CH 2) y} CH 2 O) -, or _{- ((CH 2) y CH} (CH 3) O) - represents, y each independently represents an integer of 0 to 10, and X each independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxyl group.
In formula (i), the total of (meth)acryloyl groups is 3 or 4, m each independently represents an integer of 0 to 10, and the sum of each m is an integer of 0 to 40. However, when the sum of each m is 0, any one of X is a carboxyl group.
In formula (ii), the total number of (meth)acryloyl groups is 5 or 6, n each independently represents an integer of 0 to 10, and the sum of each n is an integer of 0 to 60. However, when the sum 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, more preferably an integer of 0 to 4. Moreover, the sum of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
In formula (ii), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Moreover, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
Formula (i) or formula (ii) in the _{- ((CH 2) y CH} 2 O) - or _{- ((CH 2) y CH} (CH 3) O) - , the terminal oxygen atom side bonded to X The preferred form is In particular, in the formula (ii), a form in which all six X are acryloyl groups is preferable.

Examples of commercially available products of the compounds represented by the formulas (i) and (ii) include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer Co., Ltd., and Pentylene, manufactured by Nippon Kayaku Co., Ltd. Examples thereof include DPCA-60, which is a 6-functional acrylate having 6 oxy chains, and TPA-330, which is a 3-functional acrylate having 3 isobutyleneoxy chains.

Examples of the radically polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, and Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, use of addition-polymerizable monomers having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909 and JP-A-1-105238. You can also
As commercially available products, urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (Shin Nakamura) Chemical Industry Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha Chemical Co., Ltd.). Manufactured by NOF CORPORATION, and Blemmer PME400 (manufactured by NOF CORPORATION).

From the viewpoint of heat resistance, the radically polymerizable compound preferably has a partial structure represented by the following formula. However, * in the formula is a connecting hand.

Specific examples of the compound having the partial structure include, for example, trimethylolpropane tri(meth)acrylate, isocyanuric acid ethylene oxide-modified di(meth)acrylate, isocyanuric acid ethylene oxide-modified tri(meth)acrylate, and pentaerythritol tri(meth)acrylate. ) Acrylate, pentaerythritol tetra(meth)acrylate, dimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tetramethylolmethane tetra(meth)acrylate and the like. ..

In the resin composition, the content of the radically polymerizable compound 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% by mass or more. The upper limit is more preferably 30% by mass or less.
The mass ratio of the polyimide precursor and the radically polymerizable compound (polyimide precursor/radical polymerizable compound) is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, and 90/10. 50/50 is more preferable. When the mass ratio of the polyimide precursor and the radically polymerizable compound is in the above range, a cured film having excellent curability 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.

<< photopolymerization initiator >>
The resin composition in the present invention preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include photocationic polymerization initiators and photoradical polymerization initiators, and photoradical polymerization initiators are preferable. When the resin composition in the present invention contains a photoradical polymerization initiator, the resin composition is applied to a support such as a semiconductor wafer to form a resin composition layer, and then the resin composition layer is irradiated with light to cause radicals. Curing occurs, and the solubility in the light irradiation part can be reduced. Therefore, for example, by exposing the resin composition layer through a photomask having a pattern that masks only the electrode portion, there is an advantage that regions having different solubilities can be easily produced according to the pattern of the electrodes and the like. ..

The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, a photopolymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator which produces an active radical by causing some action with the photoexcited sensitizer. The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.

Any known compound can be used as the photopolymerization initiator. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned. For details of these, the description in paragraphs 0165 to 0182 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification. Further, examples of the ketone compound include the compounds described in paragraph 0087 of JP-A-2005-087611, and the contents thereof are incorporated in the present specification. In the commercially available product, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

As the photopolymerization initiator, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound and a metallocene compound can also be suitably used. More specifically, for example, the photopolymerization initiator described in JP-A-10-291969 and the photopolymerization initiator described in Japanese Patent No. 4225898 can also be used.
As the α-hydroxyketone 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-aminoketone compound, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the α-aminoketone compound, the compound described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source of 365 nm or 405 nm can also be used.
Examples of the acylphosphine compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: all manufactured by BASF) can be used.
IRGACURE-784 (made by BASF) etc. are illustrated as a metallocene compound.

An oxime compound is more preferable as the photopolymerization initiator. By using an oxime compound, the exposure latitude can be improved more effectively. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a thermal base generator.
As specific examples of the oxime compound, the compounds described in JP 2001-233842 A, the compounds described in JP 2000-80068 A, and the compounds described in JP 2006-342166 A can be used. Preferred oxime compounds include, for example, 3-benzooxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxy Examples thereof include imino-1-phenylpropan-1-one.

As commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA, Inc., JP 2012-14052 A). The polymerization initiator 2) is also preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Power Electronics Co., Ltd.), ADEKA ARKUL'S NCI-831 and ADEKA ARKRUZ NCI-930 (manufactured by ADEKA) can also be used. Also, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used. Furthermore, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP-A-2014-500852, and JP 2013-2013 A. The compound (C-3) etc. which are described in paragraph 0101 of 164471 gazette are mentioned.
Examples of the most preferable oxime compound include oxime compounds having a specific substituent shown in JP-A 2007-269779 and oxime compounds having a thioaryl group shown in JP-A 2009-191061.

As the photopolymerization initiator, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl. At least selected from imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds. One kind is preferable, and from trihalomethyltriazine compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds. At least one selected from the above is more preferable, and at least one selected from trihalomethyltriazine compounds, α-hydroxyketone compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers and benzophenone compounds is further preferable, and metallocene compounds or oxime compounds are preferred. Is more preferable, and an oxime compound is particularly preferable.

Further, the photopolymerization initiator is N,N′-tetraalkyl-4,4′-diaminobenzophenone, 2-benzyl-, such as benzophenone, N,N′-tetramethyl-4,4′-diaminobenzophenone (Michler's ketone) or the like. Aromatic ketones such as 2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, alkylanthraquinones, etc. It is also possible to use quinones condensed with an aromatic ring, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyl dimethyl ketal. Moreover, the compound represented by the following formula (I) can also be used.
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; a phenyl group; C1-C20 alkyl group, C1-C12 alkoxy group, halogen atom, cyclopentyl group, cyclohexyl group, C2-C12 alkenyl group, C2-C2 interrupted by one or more oxygen atoms A phenyl group substituted with at least one of an alkyl group having 18 and an alkyl group having 1 to 4 carbon atoms; or biphenylyl, and R ⁵¹ is a group represented by the formula (II), or the same as R ⁵⁰ R ^{52 to} R ⁵⁴ each independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or halogen.
Formula (II)
In the formula, R ^{55 to} R ⁵⁷ are the same as R ^{52 to} R ⁵⁴ of the above formula (I).

In addition, as the photopolymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication WO2015/125469 can also be used.

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

<< polymerization inhibitor >>
The resin composition in the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, p-benzoquinone, diphenyl-p-benzoquinone, 4,4′-thiobis. (3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N -Phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso -2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis (4-Hydroxy-3,5-tert-butyl)phenylmethane and the like are preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication 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 mass% with respect to the total solid content of the resin composition. Only one type of polymerization inhibitor may be used, or two or more types may be used. When two or more polymerization inhibitors are used, the total amount is preferably within the above range.

<< Photobase generator >>
The resin composition in the present invention may contain a photobase generator. The photo-base generator is a substance that generates a base upon exposure to light, and does not show activity under normal conditions at room temperature and pressure, but when irradiated with electromagnetic waves and heated as an external stimulus, a base (basic substance ) Is not particularly limited as long as it causes

The content of the photobase generator is not particularly limited as long as it can form a desired pattern, and can be a general content. The content of the photobase generator is preferably in the range of 0.01 parts by mass or more and less than 30 parts by mass, and in the range of 0.05 parts by mass to 25 parts by mass with respect to 100 parts by mass of the resin composition. Is more preferable, and the range of 0.1 to 20 parts by mass is further preferable.

In the present invention, a known compound can be used as the photobase generator. For example, M. Shirai, and M.M. Tsunooka, Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kadooka, Polymer Processing, 46, 2 (1997); Kutal, Coord. Chem. Rev. , 211, 353 (2001); Kaneko, A.; Sarker, and D.M. Neckers, Chem. Mater. H., 11, 170 (1999); Tachi, M.; Shirai, and M.M. Tsunooka, J.; Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K.K. Graziano, J.; Photopolym. Sci. Technol. , 3, 419 (1990); Tsunooka, H.; Tachi, and S.M. Yoshitaka, J.; Photopolym. Sci. Technol. K., 9, 13 (1996); Suyama, H.; Araki, M.; Shirai, J.; Photopolym. Sci. Technol. , 19, 81 (2006), a compound having a structure such as a transition metal compound complex and an ammonium salt, and a compound hidden by forming a salt with a carboxylic acid at an amidine moiety. , An ionic compound neutralized by forming a salt with the base component, or a nonionic compound such as a carbamate derivative, an oxime ester derivative, or an acyl compound in which the base component is hidden by a urethane bond or an oxime bond. Can be mentioned. It is also preferable to use WPBG-266 (manufactured by Wako Pure Chemical Industries, Ltd.).

The basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines.
The generated basic substance is preferably a compound having an amino group with higher basicity. This is because it has a strong catalytic action on the dehydration condensation reaction or the like in the imidization of the polyimide precursor, and the addition of a smaller amount enables the manifestation of the catalytic effect in the dehydration condensation reaction or the like at a lower temperature. That is, since the generated basic substance has a large catalytic effect, the apparent sensitivity of the resin composition is improved. From the viewpoint of the above-mentioned catalytic effect, amidine and aliphatic amine are preferable.

The photobase generator is preferably a photobase generator containing no salt in its structure. It is preferred that there is no charge on the nitrogen atom of the base moiety generated in the photobase generator. In the photobase generator, the generated base is preferably hidden by using a covalent bond, and the mechanism of generation of the base is such that the covalent bond between the nitrogen atom and the adjacent atom of the generated base moiety is cleaved. It is more preferable that the compound generate a base. When the photobase generator does not contain a salt in the structure, the photobase generator can be neutralized, so that the solvent solubility is good and the pot life is improved. For these reasons, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.

Further, for the reasons described above, it is preferable that the photobase generator has a latent base generated as described above using a covalent bond. Further, it is more preferable that the generated base is hidden using an amide bond, a carbamate bond or an oxime bond.

Examples of the photobase generator include photobase generators having a cinnamic acid amide structure described in JP 2009-80452 A and WO 2009/123122 A, JP 2006-189591 A and JP 2008-247747 A. It is also possible to use the photobase generator having a carbamate structure described in the publication, and the photobase generator having an oxime structure and a carbamoyloxime structure described in JP2007-249013A and JP2008-003581A. ..

In addition, as the photobase generator, compounds described in paragraphs Nos. 0185 to 0188, 0199 to 0200 and 0202 of JP2012-93746A, compounds described in paragraphs 0022 to 0069 of JP2013-194205A are disclosed. , JP-A-2013-204019, paragraphs 0026 to 0074, and WO 2010/064631, paragraphs 0052.

<< thermal base generator >>
The resin composition in the present invention may contain a thermal base generator. The thermal base generator includes at least one selected from an acidic compound (A1) that generates a base when heated to 40° C. or higher, and an ammonium salt (A2) having an anion having a pKa1 of 0 to 4 and an ammonium cation. It is preferable. Here, the pKa1, shows logarithmic representation of the dissociation constant of the first proton polyvalent acid (Ka) of _(-Log 10 Ka).
Since the acidic compound (A1) and the ammonium salt (A2) generate a base when heated, the base generated from these compounds can accelerate the cyclization reaction of the polyimide precursor or the like, and the ring of the polyimide precursor or the like can be promoted. Can be carried out at low temperature. Further, these compounds, even when coexisting with a polyimide precursor or the like that is cyclized and cured by a base, since the cyclization of the polyimide precursor or the like hardly progresses without heating, a resin composition having excellent storage stability. Can be prepared.
In the present specification, the acidic compound means that 1 g of the compound is collected in a container, 50 mL of a mixed liquid of ion-exchanged water and tetrahydrofuran (mass ratio is water/tetrahydrofuran=1/4) is added, and the mixture is allowed to stand at room temperature for 1 hour. By stirring, the resulting solution means a compound having a pH value of less than 7 measured at 20° C. using a pH meter.

The base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40°C or higher, more preferably 120 to 200°C. The upper limit of the base generation temperature is more preferably 190°C or lower, further preferably 180°C or lower, and further preferably 165°C or lower. The lower limit of the base generation temperature is more preferably 130°C or higher, and even more preferably 135°C or higher.
When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120° C. or higher, a base is less likely to be generated during storage, so that a resin composition having excellent stability can be prepared. If the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200° C. or lower, the cyclization temperature of the polyimide precursor or the like can be lowered. For the base generation temperature, for example, using differential scanning calorimetry, the compound is heated in a pressure-resistant capsule at 5° C./min to 250° C., the peak temperature of the lowest exothermic peak is read, and the peak temperature is measured as the base generation temperature. can do.

The base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Since the tertiary amine has high basicity, the cyclization temperature of the polyimide precursor or the like can be further lowered. The boiling point of the base generated by the thermal base 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 2000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. The molecular weight value is a theoretical value obtained from the structural formula.

The acidic compound (A1) preferably contains at least one selected from ammonium salts and compounds represented by the formula (A1) described later.

The ammonium salt (A2) is preferably an acidic compound. The 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 40°C or higher (preferably 120 to 200°C). ) It may be a compound other than an acidic compound that generates a base when heated to.

In the present invention, the ammonium salt means a salt of an ammonium cation represented by the following formula (101) or formula (102) and an anion. The anion may be bound to any part of the ammonium cation via a covalent bond and may be outside the molecule of the ammonium cation, but is preferably outside the molecule of the ammonium cation. In addition, the anion being outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bound to each other via a covalent bond. Hereinafter, the anion outside the molecule of the cation portion is also referred to as a counter anion.
In the above formula, R ^{1 to} R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and formula R ⁷ represents a hydrocarbon group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁵ and R ⁷ may be bonded to each other to form a ring.

In the present invention, the ammonium salt preferably has an anion having a pKa1 of 0 to 4 and an ammonium cation. The upper limit of pKa1 of the anion is more preferably 3.5 or less, still more preferably 3.2 or less. The lower limit is more preferably 0.5 or more, still more preferably 1.0 or more. When the pKa1 of the anion is in the above range, the polyimide precursor or 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 thermal base generator is good, the generation of base without heating can be suppressed, and the stability of the resin composition is good. When pKa1 is 0 or more, the generated base is hardly neutralized, and the cyclization efficiency of the polyimide precursor or the like is good.
The type of anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and the carboxylate anion is more preferable because the stability of the salt and the thermal decomposability can both be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
The carboxylic acid anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion. According to this aspect, the thermal base generator can further improve the stability, curability, and developability of the resin composition. In particular, the stability, curability and developability of the resin composition can be further improved by using the anion of divalent carboxylic acid.
In the present invention, the carboxylic acid anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less. The pKa1 is more preferably 3.5 or less, still more preferably 3.2 or less. According to this aspect, the stability of the resin composition can be further improved.
Here, pKa1 represents the logarithm of the reciprocal of the first dissociation constant of acid, and is referred to as Determination of Organic Structures by Physical Methods (Author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Compilation: Braude, EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, RMC et al; Oxford, Clarendon Press, 1959) can be referred to. For compounds not described in these documents, the value calculated from the structural formula using ACD/pKa (manufactured by ACD/Labs) is used.

In the present invention, the carboxylate anion is preferably represented by the following formula (X1).
In the formula (X1), EWG represents an electron-withdrawing group.

In the present invention, the electron-withdrawing group means that the Hammett's substituent constant σm shows a positive value. Here, σm is a review by Yuho Tono, Journal of Organic Synthetic Chemistry, Vol. 23, No. 8 (1965) P. 631-642. The electron withdrawing group of the present invention is not limited to the substituents described in the above documents.
Examples of the substituent in which σm exhibits a positive value include, for example, CF ₃ group (σm=0.43), CF ₃ CO group (σm=0.63), and HC≡C group (σm=0.21). , 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), and the like. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

In the present invention, EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
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, the carboxylate anion is also preferably represented by the following formula (X).
In formula (X), L ¹⁰ represents a single bond, or a divalent linking group selected from an alkylene group, an alkenylene group, an arylene group, —NR ^X — and a combination thereof, and R ^X represents a hydrogen atom, It represents an alkyl group, an alkenyl group or an aryl group.

Specific examples of the carboxylate anion include maleate anion, phthalate anion, N-phenyliminodiacetic acid anion and oxalate anion. These can be preferably used.

The ammonium cation is preferably represented by any of the following general formulas (Y1-1) to (Y1-6).

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,
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 heterocycle. The ring may be monocyclic or polycyclic. The linking group when the above groups are bonded to each other to form a ring is selected from the group consisting of —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aryl group and a combination thereof. The divalent linking group selected may be mentioned. Specific examples of the ring formed include, for example, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyrazine ring, morpholine ring, thiazine ring, indole ring, isoindole. Ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline 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), represented by formula (Y1-1) or formula (Y1-2), and R ¹⁰¹ is aryl. A structure which is a group is more preferable, and a structure represented by the formula (Y1-1) in which R ¹⁰¹ is an aryl group is particularly preferable. That is, in the present invention, the ammonium cation is more preferably represented by the following formula (Y).
In formula (Y), Ar ¹⁰ represents an aromatic group, R ^{11 to} R ¹⁵ each independently represents a hydrogen atom or a hydrocarbon group, and R ¹⁴ and R ¹⁵ are 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, but an alkyl group, an alkenyl group or an aryl group is preferable.
R ¹¹ and R ¹² are preferably hydrogen atoms.

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

R ¹⁴ and R ¹⁵ may combine with each other to form a ring. Examples of the ring include a cycloaliphatic (non-aromatic hydrocarbon ring), an aromatic ring and a heterocycle. The ring may be monocyclic or polycyclic. The linking group when R ¹⁴ and R ¹⁵ are combined to form a ring includes —CO—, —O—, —NH—, a divalent aliphatic group, a divalent aromatic group and a combination thereof. A divalent linking group selected from the group consisting of Specific examples of the ring formed include, for example, pyrrolidine ring, pyrrole ring, piperidine ring, pyridine ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, pyrazine ring, morpholine ring, thiazine ring, indole ring, isoindole. Ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline ring, carbazole ring and the like.

R ¹³ to R ^{15 is} either ^{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) It is preferable that R ¹⁴ and R ¹⁵ are each independently an alkyl group having 1 to 3 carbon atoms (more preferably 1 or 2 carbon atoms). According to this aspect, it is possible to easily generate the amine species having a high boiling point.
From the viewpoint of the basicity and boiling point of the generated amine species, the total number of carbon atoms of R ¹³ , R ¹⁴ and R ¹⁵ is preferably 7-30, more preferably 10-20.
In addition, 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, because the amine species having a high boiling point is easily generated.

Further, as an embodiment for further improving the adhesion to a metal layer such as copper, in the formula (Y), R ¹³ and R ¹⁴ are a methyl group or an ethyl group, and R ¹⁵ is a direct group having 5 or more carbon atoms. Examples thereof include a form of a chain, branched or cyclic alkyl group or an aryl group. R ¹³ and R ¹⁴ are methyl groups, and 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. Are preferred, R ¹³ and R ¹⁴ are methyl groups, and R ¹⁵ is 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. Is more preferable. By reducing the hydrophobicity of the amine species in this way, the affinity between the metal layer and the polyimide or the like can be increased even when the amine is attached to the metal layer such as copper.

In the present invention, the acidic compound is also preferably a compound represented by the following formula (A1). This compound is acidic at room temperature, but when heated, the carboxyl group is decarboxylated or is lost by cyclodehydration, and the amine site that had been neutralized and inactivated until then becomes active. It becomes sex. The formula (A1) will be described below.

Formula (A1)
In formula (A1), A ¹ represents a p-valent organic group, R ¹ represents a monovalent organic group, L ¹ represents a (m+1)-valent linking group, and m represents an integer of 1 or more, p represents an integer of 1 or more.

In formula (A1), A ¹ represents a p-valent organic group. Examples of the organic group include an aliphatic group and an aromatic group, and the aromatic group is preferable. By using A ¹ as an aromatic group, a base having a high boiling point can be easily generated at a lower temperature. By increasing the boiling point of the generated base, volatilization or decomposition of the polyimide precursor or the like due to heating during curing can be suppressed, and cyclization of the polyimide precursor or the like can be more effectively promoted.
Examples of the monovalent aliphatic group include an alkyl group and an alkenyl group.
1-30 are preferable, as for carbon number of an alkyl group, 1-20 are more preferable, and 1-10 are more preferable. The alkyl group may be linear, branched or cyclic. The alkyl group may have a substituent or may be unsubstituted. Specific examples of the alkyl group include a methyl group, an ethyl group, a tert-butyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and an adamantyl group.
2-30 are preferable, as for carbon number of an alkenyl group, 2-20 are more preferable, and 2-10 are more preferable. The alkenyl group may be linear, branched or 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 valent aliphatic group include groups obtained by removing one or more hydrogen atoms from the above 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. Substitution is preferred. Specific examples of the aromatic group include a benzene ring group, a naphthalene ring group, a pentalene ring group, an indene ring group, an azulene ring group, a heptalene ring group, an indacene ring group, a perylene ring group, a pentacene ring group, an acenaphthene ring group and a phenanthrene ring group. Ring group, anthracene ring group, naphthacene ring group, chrysene 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, indolizine ring group, indole ring group, benzofuran ring group, benzothiophene ring group, isobenzofuran ring group, quinolidine ring group, quinoline ring group, phthalazine ring group Group, naphthyridine ring group, quinoxaline ring group, quinoxazoline ring group, isoquinoline ring group, carbazole ring group, phenanthridine ring group, acridine ring group, phenanthroline ring group, thianthrene ring group, chromene ring group, xanthene ring group, phenoxati Examples thereof include an in ring group, a phenothiazine ring group, and a phenazine ring group, and a benzene ring group is most preferable.
In the aromatic group, a plurality of aromatic rings may be linked via a single bond or a linking group described below. As the linking group, for example, an alkylene group is preferable. The alkylene group is preferably linear or branched. Specific examples of the group in which a plurality of aromatic rings are linked through a single bond or a linking group include a biphenyl group, a diphenylmethane group, a diphenylpropane group, a diphenylisopropane group, a triphenylmethane group, and a tetraphenylmethane group. ..

Examples of the substituent which the organic group represented by A ¹ may have include, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a methoxy group, an ethoxy group, a tert-butoxy group and the like. Alkoxy group; aryloxy group such as phenoxy group and p-tolyloxy group; alkoxycarbonyl group such as methoxycarbonyl group and butoxycarbonyl group; aryloxycarbonyl group such as phenoxycarbonyl group; acetoxy group, propionyloxy group and benzoyloxy group Acyloxy group; Acyl group such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxaryl group; alkylsulfanyl group such as methylsulfanyl group and tert-butylsulfanyl group; phenylsulfanyl group and p-tolylsulfanyl group Arylsulfanyl group such as; alkyl group such as methyl group, ethyl group, tert-butyl group and dodecyl group; halogenated alkyl group such as fluoroalkyl group; cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclo group such as adamantyl group Alkyl group; aryl group such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group and phenanthryl group; hydroxyl group; carboxyl group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; aryl Aminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group; diarylamino group; thioxy group; or a combination thereof.

L ¹ represents a (m+1)-valent linking group. The linking group is not particularly limited, and includes —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group (preferably a group having 1 to 10 carbon atoms). A chain or branched alkylene group), a cycloalkylene group (preferably a cycloalkylene group having 3 to 10 carbon atoms), an alkenylene group (preferably a straight chain or branched alkenylene group having 210 carbon atoms), or a linking group in which a plurality thereof are linked. And so on. The total number of carbon atoms in the linking group is preferably 3 or less. The linking group is preferably an alkylene group, a cycloalkylene group or an alkenylene group, more preferably a linear or branched alkylene group, further preferably a linear alkylene group, particularly preferably an ethylene group or a methylene group, most preferably a methylene group.

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 in A ¹ above. The monovalent organic group represented by R ¹ may have a substituent. Examples of the substituent include those mentioned 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)-valent linking group, and n represents an integer of 1 or more.
Examples of the linking group represented by L ² include the groups described for L ¹ described above, the preferred ranges are also the same, an ethylene group or a methylene group is particularly preferred, and a methylene group is most preferred.
n represents an integer of 1 or more, preferably 1 or 2, and more preferably 1. The upper limit of n is the maximum number of substituents that the linking group represented by L ² can have. When n is 1, heating at 200° C. or lower tends to generate a tertiary amine having a high boiling point. Furthermore, the stability of the resin composition can be improved.

m represents an integer of 1 or more, preferably 1 or 2, and more preferably 1. The upper limit of m is the maximum number of substituents that the linking group represented by L ¹ can have. If m is 1, heating at 200° C. or lower tends to generate a tertiary amine having a high boiling point. Furthermore, the stability of the resin composition can be improved.
p represents an integer of 1 or more, preferably 1 or 2, and more preferably 1. The upper limit of p is the maximum number of substituents that the organic group represented by A ¹ can take. When p is 1, heating at 200° C. or lower tends to generate a tertiary amine having a high boiling point.

In the present invention, the compound represented by the formula (A1) is preferably a compound represented by the following formula (1a).
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, and m represents an integer of 1 or more. , N represents an integer of 1 or more, and p represents an integer of 1 or more.
A ¹ , L ¹ , L ² , m, n and p in the general formula (1a) have the same meanings as the ranges described in the general formula (A1), and the preferred ranges are also the same.

In the present invention, the compound represented by formula (A1) is preferably N-aryliminodiacetic acid. In N-aryliminodiacetic acid, A ¹ in the general formula (A1) is an aromatic group, L ¹ and L ² are methylene groups, m is 1, n is 1, and p is 1 It is a compound. N-aryliminodiacetic acid tends to generate a tertiary amine having a high boiling point at 120 to 200°C.

Hereinafter, specific examples of the thermal base generator will be described, but the present invention is not limited thereto. These may be used alone or in admixture of two or more. Me in the following formulas 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) and (A-18) to (A-26) are more preferable, and (A-1) to (A-9) and (A-18). )-(A-21), (A-23), and (A-24) are more preferable.

As the thermal base generator used in the present invention, compounds described in Japanese Patent Application No. 2015-034388, paragraphs 0015 to 0055 are also preferably used, and the contents thereof are incorporated in the present specification.

When the thermal base generator is used, the content of the thermal base generator in the resin composition is preferably 0.1 to 50 mass% with respect to the total solid content of the resin composition. The lower limit is more preferably 0.5% by mass or more, still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less.
The thermal base generator can use 1 type(s) or 2 or more types. When two or more kinds are used, the total amount is preferably within the above range.

<< thermal radical polymerization initiator >>
The resin composition in the present 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 radicals by the energy of heat and initiates or accelerates a polymerization reaction such as a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polymerizable compound or the like can be promoted when the cyclization reaction of the polyimide precursor or the like is promoted. Further, when the polyimide precursor contains a radically polymerizable group, the polymerization reaction of the polyimide precursor can be progressed together with the cyclization of the polyimide precursor, so that higher heat resistance can be achieved.
As the thermal radical polymerization initiator, aromatic ketones, onium salt compounds, peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogens. Examples thereof include compounds having a bond and azo compounds. Among them, peroxides or azo compounds are more preferable, and peroxides are particularly preferable.
The thermal radical polymerization initiator used in the present invention preferably has a 10-hour half-life temperature of 90 to 130°C, more preferably 100 to 120°C.
Specific examples thereof include the compounds described in paragraph Nos. 0074 to 0118 of JP 2008-63554 A.
Among commercially available products, Perbutyl Z and Perkmill 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 0.1 to 30% by mass based on the total solid content of the resin composition. Is more preferable, and 0.1 to 20 mass% is particularly preferable. Further, the thermal radical polymerization initiator is preferably contained in an amount of 0.1 to 50 parts by mass, more preferably 0.5 to 30 parts by mass, relative to 100 parts by mass of the polymerizable compound. According to this aspect, it is easy to form a cured film having more excellent heat resistance. Only one type of thermal radical polymerization initiator may be used, or two or more types may be used. When two or more thermal radical polymerization initiators are used, the total is preferably within the above range.

<< Anticorrosion >>
The resin composition of the present invention preferably contains a rust preventive agent. When the resin composition contains the rust preventive agent, it is possible to effectively prevent the metal ions derived from the metal layer (metal wiring) from moving into the resin composition layer. As the rust preventive agent, the rust preventive agent described in paragraph 0094 of JP2013-15701A, the compound described in paragraphs 0073 to 0076 of JP2009-283711A, and the paragraph 0052 of JP2011-59656A can be used. And the compounds described in paragraphs 0114, 0116, and 0118 of JP 2012-194520 A and the like can be used. Specifically, heterocycles (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine Ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and mercapto groups, hindered phenol compounds, salicylic acid derivative compounds, hydrazide Examples include derivative compounds. Of these, triazole compounds such as triazole and benzotriazole, and tetrazole compounds such as tetrazole and benzotetrazole are preferable, and 1,2,4-triazole, 1,2,3-benzotriazole and 5-methyl-1H-benzotriazole are preferable. 1H-tetrazole, 5-methyl-1H-tetrazole and 5-phenyl-1H-tetrazole are more preferable, and 1H-tetrazole is the most preferable. As commercially available products, KEMITEC BT-C (1,2,3-benzotriazole, manufactured by Chemipro Kasei Co., Ltd.), 1HT (1H-tetrazole, manufactured by Toyobo Co., Ltd.), P5T (manufactured by Toyobo Co., Ltd., 5- (Phenyl-1H-tetrazole) and the like. It is also preferable to use KEMINOX 179 (produced by Chemipro Kasei Co., Ltd.).

When the resin composition contains a rust preventive, the content of the rust preventive is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the resin. Only one kind of rust preventive agent may be used, or two or more kinds thereof may be used. When two or more kinds are used, it is preferable that the total is within the above range.

<< Silane coupling agent >>
The resin composition in the present invention preferably contains a silane coupling agent in order to improve the adhesiveness with a metal material used for electrodes and wiring. Examples of the silane coupling agent include the compounds described in paragraphs 0062 to 0073 of JP2014-191002A, the compounds described in paragraphs 0063 to 0071 of WO2011/080992A1, and JP2012-191252A. Examples include the compounds described in paragraphs 0060 to 0061, the compounds described in paragraphs 0045 to 0052 of JP-A-2014-41264, and the compounds described in paragraph 0055 of International Publication WO2014/097594. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Further, as the silane coupling agent, it is also preferable to use 2-((3-(triethoxysilyl)propyl)carbamoyl)benzoic acid, triethoxysilylpropylmaleamic acid, or the following compounds. 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) or the like can also be used.

The content of the silane coupling agent is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the resin. When the content of the silane coupling agent is 0.1 part by mass or more, the adhesion of the film obtained to the metal layer is good, and the content of the silane coupling agent is 30 parts by mass or less. The heat resistance and mechanical properties of the film are improved. 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 within the above range.

<<solvent>>
In the present invention, when the resin composition is layered by coating, it is preferable to add a solvent to the resin composition. Any known solvent may be used as the solvent. Examples thereof include compounds such as esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.
Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone. , Δ-valerolactone, alkyl alkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. )), 3-alkyloxypropionic acid alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy) Methyl propionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc.) (For example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methylpropionic acid Methyl and ethyl 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, pyruvate Suitable examples include propyl, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like.
Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol. Preference is given to monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.
Preferable examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like.
Preferable examples of the aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.
Preferable examples of the sulfoxides include dimethyl sulfoxide.

From the viewpoint of improving the properties of the coated surface, the solvent is preferably a mixture of two or more kinds. Among them, 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 A mixed solution composed of two or more selected from dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

When the resin composition has a solvent, the content of the solvent is preferably 5 to 80% by mass, and 5 to 70% by mass, from the viewpoint of coatability. More preferably, 10-60 mass% is especially preferable. The solvent content may be adjusted according to the desired thickness and coating method. For example, when the coating method is spin coating or slit coating, the content of the solvent having the solid content concentration in the above range is preferable. In the case of spray coating, the amount is preferably 0.1% by mass to 50% by mass, and more preferably 1.0% by mass to 25% by mass. By adjusting the amount of solvent according to the coating method, a resin composition layer having a desired thickness can be uniformly formed.
Only one type of solvent may be used, or two or more types may be used. When two or more kinds of solvents are used, it is preferable that the total thereof is within the above range.
Further, the content of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide and N,N-dimethylformamide is based on the total mass of the resin composition from the viewpoint of film strength. Is less than 5% by mass, more preferably less than 1% by mass, even more preferably less than 0.5% by mass, still more preferably less than 0.1% by mass.

<<sensitizing dye>>
The resin composition in the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific actinic radiation to be in an electronically excited state. The sensitizing dye in the electronically excited state comes into contact with a thermal base generator, a photobase generator, a thermal radical polymerization initiator, a photopolymerization initiator, etc., and effects such as electron transfer, energy transfer, and heat generation. As a result, the thermal base generator, photobase generator, thermal radical polymerization initiator, and photopolymerization initiator undergo a chemical change and are decomposed to generate radicals, acids, or bases. For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present 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, based on the total solid content of the resin composition. 0.5 to 10 mass% is more preferable. The sensitizing dyes may be used alone or in combination of two or more.

<< chain transfer agent >>
The resin composition in the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, on pages 683 to 684 of the High Polymer Dictionary Third Edition (edited by The Society of Polymer Science, 2005). As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in the molecule is used. These can donate hydrogen to a radical species having low activity to generate a radical, or can generate a radical by being deprotonated after being oxidized. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazole, etc.) can be preferably used. 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 with respect to 100 parts by mass of the total solid content of the resin composition. Parts, more preferably 1 to 5 parts by mass. The chain transfer agent may be only one type or two or more types. When two or more chain transfer agents are used, the total is preferably within the above range.

<< Surfactant >>
Various surfactants may be added to the resin composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The following surfactants are also preferable.

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

<<Higher fatty acid derivative>>
In order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to the resin composition of the present invention, and the surface of the composition is dried in the course of drying after coating. It may be unevenly distributed. When the resin composition has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10 mass% with respect to the total solid content of the resin composition. Only one kind of higher fatty acid derivative may be used, or two or more kinds thereof may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.

<<Other additives>>
The resin composition in the present invention, as long as the effects of the present invention are not impaired, if necessary, various additives, for example, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, agglomerates. An inhibitor or the like can be added. 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>>>
The water content of the resin composition in the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass from the viewpoint of the properties of the coated surface.

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, particularly preferably less than 0.5 mass ppm, from the viewpoint of insulation properties. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium and nickel. When a plurality of metals are contained, the total of these metals is preferably within the above range.
Further, as a method for reducing the metal impurities unintentionally included in the resin composition, a raw material having a low metal content is selected as a raw material constituting the resin composition, and a filter for the raw material constituting the resin composition is selected. Examples thereof include a method of performing filtration, a method of lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible.

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

<Preparation of resin composition>
The resin composition can be prepared by mixing the above components. The mixing method is not particularly limited and may be a conventionally known method.
Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign matters such as dust and fine particles in the resin composition. The pore size of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, still more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be washed with an organic solvent in advance. In the filter filtration step, plural kinds of filters may be connected in series or in parallel and used. When using a plurality of types of filters, filters having different pore sizes and/or materials may be used in combination. Also, various materials may be filtered multiple times. When filtration is performed a plurality of times, circulation filtration may be used. Moreover, you may pressurize and may perform filtration. When performing filtration by pressurizing, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, removal processing of impurities using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

<Method for manufacturing laminated body>
Next, a method for manufacturing the laminate of the present invention will be described. The method for manufacturing a laminated body of the present invention includes the pattern forming method of the present invention described above.

The method for producing a laminate of the present invention comprises a negative photosensitive resin composition layer forming step, an exposing step, a developing step and a heating step to form a resin layer pattern on a support, and then a metal layer forming step. The negative photosensitive resin composition layer forming step, the exposure step, the developing step and the pattern forming step of performing the heating step in this order are preferably alternately performed 2 to 7 times, and more preferably 2 to 5 times. preferable. By doing so, it is possible to manufacture a laminate having a multilayer wiring structure in which a plurality of resin layers and metal layers formed of a negative photosensitive resin composition layer are alternately laminated. In addition, in such a laminated 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, patterns with a greater difference in thickness are often formed. Moreover, the conventional method tends to require a lot of steps because the number of steps is significantly increased. Further, as the number of laminated resin layers increases, the support or the like tends to warp, and it has been difficult to maintain the uniformity of the pattern by the conventional method. On the other hand, according to the present invention, a pattern can be efficiently formed on the resin layer (negative-type photosensitive resin composition layer) even in the laminated body having such a multilayer wiring structure. Therefore, by using the pattern forming method of the present invention in the production of such a laminate, the effects of the present invention can be more easily exhibited.

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

The laminated body shown in FIG. 3 will be described. A desired pattern is formed on the resin layer 201. This 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 on the resin layer 202, and a part of the metal layer 301 is exposed from the resin layer 202. This 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 from the resin layer 202.
A resin layer 203 is formed on the metal layer 302. A desired pattern is formed on the resin layer 203, and a part of the metal layer 302 is exposed from the resin layer 203. This 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 from the resin layer 203.
A resin layer 204 is formed on the metal layer 303. A desired pattern is formed on the resin layer 204, and a part of the metal layer 303 is exposed from the resin layer 204. Further, in FIG. 3, a part of the metal layer 302 is also exposed from the resin layer 204.
In this laminated body, the resin layers 201 to 204 function as insulating films, and the metal layers 301 to 303 function as wiring layers. Such a laminated body can be preferably used as a rewiring layer in an electronic device.

<Method of manufacturing electronic device>
Next, a method for manufacturing the electronic device of the present invention will be described. The method for manufacturing an electronic device of 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 the drawings. The electronic device 100 shown in FIG. 4 is a so-called three-dimensional mounting device, and a laminated body 101 in which a plurality of semiconductor elements (semiconductor chips) 101 a to 101 d are laminated is arranged on a wiring board 120. In this embodiment, the case where the number of stacked semiconductor elements (semiconductor chips) is four will be mainly described, but the number of stacked semiconductor elements (semiconductor chips) is not particularly limited, and may be, for example, 2 It may be a layer, 8 layers, 16 layers, 32 layers or the like. Moreover, it may be one layer.

Each of the plurality of semiconductor elements 101a to 101d is made of 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 in which a semiconductor element 101a having no through electrodes and semiconductor elements 101b to 101d having through electrodes 102b to 102d are flip-chip connected.
That is, the electrode pad of the semiconductor element 101a having no through electrode and the connection pad on the semiconductor element 101a side of the semiconductor element 101b having the through electrode 102b adjacent thereto are connected to each other by the metal bump 103a such as a solder bump. The connection pad on the other side of the semiconductor element 101b having the electrode 102b is connected to the connection pad on the semiconductor element 101b side of the semiconductor element 101c having the through electrode 102c adjacent thereto by a metal bump 103b such as a solder bump. Similarly, the connection pad on the other side of the semiconductor element 101c having the through electrode 102c is connected to the connection pad on the semiconductor element 101c side of the semiconductor element 101d having the through electrode 102d adjacent thereto by the metal bump 103c such as a solder bump. ing.

An underfill layer 110 is formed in the gap between the semiconductor elements 101a to 101d, and the semiconductor elements 101a to 101d are stacked with the underfill layer 110 interposed therebetween.

The laminated body 101 is laminated on the wiring board 120.
As the wiring board 120, for example, a multilayer wiring board using an insulating substrate such as a resin substrate, a ceramics substrate, or a glass substrate as a base material is used. Examples of the wiring substrate 120 to which the resin substrate is applied include a multilayer copper clad laminate (multilayer printed wiring board).

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

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist. In addition, "%" and "parts" are based on mass unless otherwise specified. NMR is an abbreviation for nuclear magnetic resonance.

(Synthesis example 1)
[Synthesis of polyimide precursor (P-1: polyimide precursor having no radically polymerizable group) from pyromellitic dianhydride, 4,4′-oxydianiline and benzyl alcohol]
14.06 g (64.5 mmol) of pyromellitic dianhydride (dried 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 over molecular sieves. The suspension was heated at 100° C. for 3 hours. A clear solution was obtained a few minutes after the heating was started. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) pyridine and 90 ml N-methylpyrrolidone were added. The reaction mixture was then cooled to −10° C. and 16.12 g (135.5 mmol) SOCl ₂ was added over 10 minutes keeping the temperature at −10±4° C. The viscosity increased during the addition of SOCl ₂ . After diluting with 50 ml N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution of 11.08 g (58.7 mmol) of 4,4′-oxydianiline dissolved in 100 ml of N-methylpyrrolidone was added dropwise to the reaction mixture at 20 to 23° C. over 20 minutes. The reaction mixture was then stirred overnight at room temperature. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was collected by filtration, added again to 4 liters of water, stirred for another 30 minutes, and filtered again. Then, the obtained polyimide precursor was dried under reduced pressure at 45° C. for 3 days to obtain a polyimide precursor (P-1) containing a repeating unit represented by the following formula.

(Synthesis example 2)
[Synthesis of polyimide precursor (P-2: polyimide precursor having radically polymerizable group) from pyromellitic dianhydride, 4,4'-oxydianiline and 2-hydroxyethyl methacrylate]
14.06 g (64.5 mmol) pyromellitic dianhydride (dried at 140° C. for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g hydroquinone, 10 0.7 g of pyridine and 140 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60° C. for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Then, after chlorinating the obtained diester with SOCl ₂ , it was converted into a polyimide precursor with 4,4′-oxydianiline in the same manner as in Synthesis Example 1, and the following formula was used in the same manner as in Synthesis Example 1. A polyimide precursor (P-2) containing a repeating unit represented by

(Synthesis example 3)
[Synthesis of polyimide precursor (P-3: polyimide precursor having radically polymerizable group) from 4,4'-oxydiphthalic anhydride, 4,4'-oxydianiline and 2-hydroxyethyl methacrylate]
20.0 g (64.5 mmol) 4,4′-oxydiphthalic anhydride (dried at 140° C. for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate and 0.05 g hydroquinone , 10.7 g of pyridine and 140 g of diglyme were mixed and stirred at a temperature of 60° C. for 18 hours to prepare a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Then, after chlorinating the obtained diester with SOCl ₂ , it was converted into a polyimide precursor with 4,4′-oxydianiline in the same manner as in Synthesis Example 1, and the following formula was used in the same manner as in Synthesis Example 1. A polyimide precursor (P-3) containing a repeating unit represented by

(Synthesis example 4)
[Synthesis of polyimide precursor (P-4: polyimide precursor having carboxyl group) from 4,4'-oxydiphthalic anhydride and 4,4'-oxydianiline]
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), and another 21.43 g was dissolved. (270.9 mmol) pyridine was added and the reaction was cooled to -10 °C and 11.08 g (58.7 mmol) 4,4'-oxydiene while maintaining the temperature at -10 ± 4 °C. A solution obtained by dissolving aniline in 100 ml of NMP was added dropwise over 30 minutes, and then the reaction mixture was stirred at room temperature overnight. Then, the mixture was poured into 5 liters of water to precipitate the polyimide precursor, and the water-polyimide precursor mixture was stirred at a speed of 5000 rpm for 15 minutes. The polyimide precursor was collected by filtration, added again to 4 liters of water, stirred for another 30 minutes, and collected again by filtration. Then, the obtained polyimide precursor was dried under reduced pressure at 45° C. for 3 days to obtain a polyimide precursor (P-4) containing a repeating unit represented by the following formula.

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

<Preparation of negative photosensitive resin composition>
The components described below were mixed to prepare a negative photosensitive resin composition coating solution as a uniform solution.
(composition)
Resin: parts by mass shown in the following table Radical polymerizable compound: parts by mass shown in the following table Photoradical polymerization initiator: parts by mass shown in the following table Silane coupling agent: parts by mass shown in the following table Rust inhibitor: Parts by mass shown in the following table Polymerization inhibitor: Parts by mass shown in the following table Base generator: Parts by mass shown in the following table Solvent 1 (dimethyl sulfoxide): 100 parts by mass Solvent 2 (γ-butyrolactone): 25 parts by mass

<Evaluation of resolution of negative photosensitive composition>
A negative photosensitive resin composition was applied onto a Si substrate to form a coating film. Then, heat treatment was performed for 240 seconds using a hot plate at 100° C. to form a negative photosensitive resin composition layer having a film thickness of 15 μm. Then, using a stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.) for the negative photosensitive resin composition layer, an i-line (light having a wavelength of 365 nm was irradiated through a pattern mask having a Bayer of 15 μm square. ) was irradiated while changing the exposure dose by 100 mJ / cm ² to at 100~1000mJ / cm ^2, then, the Si substrate a negative photosensitive resin composition layer after exposure is formed spin shower developing machine (DW-30 type; manufactured by Chemitronics Co., Ltd.), placed on a horizontal rotary table and developed with cyclopentanone at 23° C. for 60 seconds to develop and remove the unexposed portion to form a pattern. .. The resolution of the negative photosensitive composition was evaluated according to the following criteria. When the exposed width of the underlying substrate was 15 μm±3 μm, a pattern having a line width of 15 μm (15 μm square pattern) was defined as resolvable.
A: The difference between the maximum value and the minimum value of the exposure amount capable of resolving 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 resolving 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 amount capable of resolving a pattern having a thickness of 15 μm and a line width of 15 μm is less than 600 mJ/cm ² .

The abbreviations listed in the table are as follows.
(resin)
P-1 to P-4: Polyimide precursors (P-1) to (P-4) synthesized in Synthesis Examples 1 to 4
P-5: Matrimid 5218 (manufactured by Huntsman Corporation, ring-closing polyimide)
P-6: Acrylic polymer (P-6) synthesized in Synthesis Example 5
P-7: Polymethylmethacrylate (Mw=15000, manufactured by Sigma-Aldrich Japan GK)

(Radical polymerizable compound)
B-1: SR209 (manufactured by Sartomer, tetraethylene glycol diacrylate)
B-2: NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated isocyanuric acid triacrylate)
B-3: A-TMMT (Shin-Nakamura Chemical Co., Ltd., pentaerythritol tetraacrylate)
B-4: A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd., dipentaerythritol hexaacrylate)

(Photo-radical polymerization initiator)
C-1: IRGACURE OXE 01 (BASF Corporation, oxime compound)
C-2: IRGACURE OXE 02 (BASF Corporation, oxime compound)
C-3: IRGACURE-784 (manufactured by BASF, metallocene compound)
C-4: ADEKA ARKUL'S NCI-831 (manufactured by ADEKA Corporation, oxime compound)

(Silane coupling agent)
D-1: KBM-602 (manufactured by Shin-Etsu Chemical Co., Ltd., silane compound having amino group)
D-2: 2-((3-(triethoxysilyl)propyl)carbamoyl)benzoic acid (manufactured by Aquila Pharmatech LLC, silane compound having a carboxyl group)
D-3: Triethoxysilylpropylmaleamic acid (manufactured by Gelest, Inc., a silane compound having a carboxyl group)

(anti-rust)
E-1: KEMITEC BT-C (1,2,3-benzotriazole, manufactured by Chemipro Kasei Co., Ltd.)
E-2:1HT (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

(Base generator)
A-1, A-21, A-40: Compounds of the following structures (thermal base generators)
A-43: WPBG-266 (manufactured by Wako Pure Chemical Industries, Ltd., photobase generator, which is also a compound that decomposes by heating to generate a base)

<Pattern forming method>
The negative type photosensitive resin composition was applied onto the Si substrate having steps shown in FIG. 5 (t1 to t8=2 μm, t9=0.5 μm, t10=0.5 μm, t11=1 μm), and the thickest part The coating speed is adjusted by adjusting the coating rotation speed so that the thickness T1 of the coating film after drying becomes 20 μm, and the coating film is heated for 240 seconds using a hot plate at 100° C. to obtain a negative photosensitive resin. A composition layer was formed. Using a stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.), the i-line (light having a wavelength of 365 nm) was applied to the negative photosensitive resin composition layer through a pattern mask having a Bayer of 15 μm square. at 100~1000mJ / cm ² by 100 mJ / cm ² was irradiated while changing the exposure amount. Then, the Si substrate on which the negative photosensitive resin composition layer after exposure is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type; manufactured by Chemitronics Co., Ltd.) and cyclo Development was carried out using pentanone at 23° C. for 60 seconds to remove the unexposed portion by development. Then, 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 underlying substrate after development was 15 μm±3 μm, a pattern having a line width of 15 μm (15 μm square pattern) was resolvable.
A: A pattern having a line width of 15 μm could be formed in a thickness range of 2 to 20 μm.
B: A pattern having a line width of 15 μm could be formed in the thickness range of 2 to 16 μm, but a pattern having a line width of 15 μm could not be formed in a portion exceeding the thickness of 16 μm.
C: A pattern having a line width of 15 μm could be formed in the thickness range of 2 to 12 μm, but a pattern having a line width of 15 μm could not be formed in a portion exceeding the thickness of 12 μm.
D: Does not correspond to any of A to C above.
A pattern having a line width of 15 μm could not be formed in any of the thicknesses of 2 to 20 μm.

As shown in the above table, the examples were able to form patterns with different thicknesses with good resolution over a wide range of exposure doses.

10: Resin layer 11: Negative photosensitive resin composition layer 20: Support 50: Mask 100: Electronic devices 101a to 101d: Semiconductor element 101: Laminates 102b to 102d: Through electrodes 103a to 103e: Metal bump 105: Re Wiring layers 110, 110a, 110b: Underfill layer 115: Insulating layer 120: Wiring substrate 120a: Surface electrodes 201-204: Resin layers 301-303: Metal layers 401-403: Groove 500: Laminated body

Claims (12)

A negative photosensitive resin composition layer is formed on a support using a negative photosensitive resin composition containing a resin and a photopolymerization initiator, and the negative photosensitive resin composition layer is exposed and developed. A pattern forming method for simultaneously forming two or more types of patterns having different thicknesses,
Among the patterns having different thicknesses formed at the same time, the thickness of the thickest pattern is 1.5 to 10 times the thickness of the thinnest pattern,
As the negative photosensitive resin composition, a negative photosensitive resin composition in which the difference between the maximum value and the minimum value of the exposure amount capable of resolving a pattern having a thickness of 15 μm and a line width of 15 μm or less is 600 mJ/cm ² or more. There use things,
The resin is a polyimide precursor,
A pattern forming method, wherein a minimum exposure amount capable of resolving a pattern having a thickness of 15 μm and a line width of 15 μm or less is 50 to 500 mJ/cm ² in the exposure of the same wavelength as the exposure . The negative photosensitive resin composition contains a radical polymerizable compound, and the mass ratio of the resin to the radical polymerizable compound in the negative photosensitive resin composition is 5:1 to 10:1. The pattern forming method according to claim 1, wherein the mass ratio of the radically polymerizable compound to the photopolymerization initiator in the photosensitive resin composition is 2:1 to 8:1. Two or more layers having different thicknesses are prepared by laminating two or more layers of the negative photosensitive resin composition layer on a support, and exposing and developing the negative type photosensitive resin composition layer having the two or more layers laminated. simultaneously forming a more patterns, a pattern forming method according to claim 1 or 2. The pattern formation according to any one of claims 1 to 3, 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. Method. The pattern forming method according to any one of claims 1 to 3, 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. As the negative photosensitive resin composition, a negative photosensitive resin composition in which a difference between the maximum value and the minimum value of the exposure amount capable of resolving a pattern having a thickness of 15 μm and a line width of 15 μm or less is 900 mJ/cm ² or more. the used pattern forming method according to any one of claims 1-5. The polyimide precursor is represented by the following formula (1), a pattern forming method according to any one of claims 1 to 6;
In the 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, R ²³ and R ²⁴ each independently represent a hydrogen atom or a monovalent organic group. The pattern forming method according to claim 7, wherein in the formula (1), at least one of R ²³ and R ²⁴ contains a radically polymerizable group. The pattern forming method according to claim 7, wherein R ²² in the formula (1) is a tetravalent group containing an aromatic ring. The pattern forming method according to claim 1, further comprising a step of forming a metal layer. A method for manufacturing a laminate, comprising the pattern forming method according to claim 1. A method for manufacturing an electronic device, comprising the pattern forming method according to claim 1.