KR102147108B1 - Method for manufacturing a laminate, a method for manufacturing a semiconductor device, and a laminate - Google Patents

Abstract

A method of manufacturing a laminate capable of suppressing delamination when a substrate, a cured film, and a metal layer are laminated; A method of manufacturing a semiconductor device; Provision of semiconductor devices. A photosensitive resin composition layer forming process in which a photosensitive resin composition is applied to a substrate to form a layer, an exposure process in which the photosensitive resin composition layer applied to the substrate is exposed, and a development treatment process in which the exposed photosensitive resin composition layer is developed And, a curing step of curing the photosensitive resin composition layer after development, and a metal layer forming step of forming a metal layer by vapor phase film formation on the surface of the photosensitive resin composition layer after the curing step, in the above order, and forming a metal layer A method for producing a laminate, wherein the temperature of the photosensitive resin composition layer after the curing step at the time is less than the glass transition temperature of the photosensitive resin composition layer after the curing step.

Description

Method for manufacturing a laminate, a method for manufacturing a semiconductor device, and a laminate

The present invention relates to a method for manufacturing a laminate, a method for manufacturing a semiconductor device, and a laminate.

Resins, such as a polyimide resin and a polybenzoxazole resin, are excellent in heat resistance and insulation, and are therefore used for insulating layers of semiconductor devices and the like.

Patent Document 1: International Publication No. WO2011/034092

Using a cured film of a resin having excellent heat resistance and insulation such as polyimide resin or polybenzoxazole resin as an interlayer insulating film for a redistribution layer of a semiconductor device, the cured film and a metal layer are laminated to prepare a redistribution layer of a semiconductor device. Is being done.

When the present inventors studied laminating a cured film and a metal layer of a resin having excellent heat resistance and insulation, such as a polyimide resin or a polybenzoxazole resin, the adhesion between the cured film and the metal layer was insufficient, and between the cured film and the metal layer. It was found that delamination occurred.

Here, in general, in the film forming method used for manufacturing a semiconductor device, by providing a barrier metal film between the substrate and the wiring layer made of copper (Cu), etc., the material constituting the wiring layer is diffused to the substrate. It is known to prevent deterioration of (see Patent Document 1).

In Patent Document 1, a substrate having fine holes or grooves formed on its surface is prepared, and a barrier metal film made of titanium or a titanium compound is formed on the substrate while the substrate temperature is set in the range of 150°C or higher and 500°C or lower. A method of forming a barrier metal film is described. According to Patent Document 1, by using the method of forming a barrier metal film having the above configuration, it is possible to reduce the occurrence of overhangs (diameters of the openings smaller than the bottoms) in the openings for patterns with high aspect ratios. It is described.

However, Patent Document 1 pays attention only to the case where a silicon oxide film is formed on the surface of a silicon wafer as a substrate. That is, Patent Document 1 does not pay attention to the delamination in the case of laminating a metal layer and a cured film of a resin having excellent heat resistance and insulating properties, such as a polyimide resin or a polybenzoxazole resin.

The problem to be solved by the present invention is to provide a method of manufacturing a laminate capable of suppressing delamination when a substrate, a cured film, and a metal layer are laminated. In addition, the problem to be solved by the present invention is to provide a method for manufacturing a semiconductor device, including a method for manufacturing a laminate. In addition, a problem to be solved by the present invention is to provide a laminate capable of suppressing delamination in the case of laminating a substrate, a cured film, and a metal layer.

Under the above problems, as a result of investigation by the present inventors, by using a gas phase film such as sputtering method at less than the glass transition temperature of a cured film of a resin having excellent heat resistance and insulation such as polyimide resin or polybenzoxazole resin. By forming a metal layer, it discovered that the said subject can be solved.

The present invention, which is a means for solving the above problem, and a preferred aspect of the present invention are as follows.

[1] a photosensitive resin composition layer forming step in which a photosensitive resin composition is applied to a substrate to form a layer,

An exposure process of exposing the photosensitive resin composition layer applied to the substrate, and

A developing treatment step of performing a development treatment on the exposed photosensitive resin composition layer, and

A curing step of curing the photosensitive resin composition layer after development, and

Including performing a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer after the curing step by vapor phase film formation in the above order,

The method for producing a laminate, wherein the temperature of the photosensitive resin composition layer after the curing step when forming the metal layer is less than the glass transition temperature of the photosensitive resin composition layer after the curing step.

[2] The method for producing a laminate according to [1], further comprising performing the photosensitive resin composition layer forming step, the exposure step, the developing treatment step, the curing step, and the metal layer forming step again in the above order.

[3] The method for producing a laminate according to [1] or [2], in which a crosslinked structure is formed by exposure to the photosensitive resin composition and solubility in an organic solvent is lowered.

[4] The laminate according to any one of [1] to [3], wherein the photosensitive resin composition contains at least one resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole. Method of making a sieve.

[5] The method for producing a laminate according to any one of [1] to [4], further comprising a second metal layer forming step of forming a second metal layer on the surface of the metal layer.

[6] The method for producing a laminate according to [5], in which the second metal layer contains copper.

[7] The method for producing a laminate according to any one of [1] to [6], in which the metal layer contains at least one of titanium, tantalum, and copper, and a compound containing at least one of them.

[8] The method for producing a laminate according to any one of [1] to [7], wherein the thickness of the metal layer formed by the metal layer forming step is 50 to 2000 nm.

[9] The method for producing a laminate according to any one of [1] to [8], wherein the residual stress measured by the laser measurement method of the photosensitive resin composition after the curing step is less than 35 MPa.

[10] The method for producing a laminate according to any one of [1] to [9], in which the photosensitive resin composition is for negative development.

[11] The curing step includes a temperature raising step of raising the temperature of the photosensitive resin composition layer, and a holding step of maintaining the same holding temperature as the final temperature reached in the temperature raising step,

The method for producing a laminate according to any one of [1] to [10], wherein the holding temperature in the holding step is 250°C or less.

[12] The method for producing a laminate according to any one of [1] to [11], wherein the temperature of the photosensitive resin composition layer at the time of forming the metal layer is 30°C or more lower than the glass transition temperature of the photosensitive resin composition layer.

[13] A method for manufacturing a semiconductor element, including the method for manufacturing a laminate according to any one of [1] to [12].

[14] having a substrate, a pattern cured film, and a metal layer positioned on the surface of the pattern cured film,

The patterned cured film contains polyimide or polybenzoxazole,

A laminate in which the penetration length of the metal constituting the metal layer positioned on the surface of the pattern cured film into the pattern cured film is 130 nm or less from the surface of the pattern cured film.

[15] A laminate produced by the method for producing a laminate according to any one of [1] to [12].

[16] A semiconductor device manufactured by the method for manufacturing a semiconductor device according to [13].

Advantageous Effects of Invention According to the present invention, it is possible to provide a method for producing a laminate capable of suppressing delamination when a substrate, a cured film, and a metal layer are laminated. Moreover, according to the present invention, it is possible to provide a method for manufacturing a semiconductor device including the method for manufacturing a laminate of the present invention. Further, according to the present invention, it is possible to provide a laminate capable of suppressing delamination when a substrate, a cured film, and a metal layer are laminated.

1 is a schematic diagram showing a configuration of an embodiment of a semiconductor element.
2 is a schematic diagram showing the configuration of an embodiment of a laminate obtained by the method for producing a laminate of the present invention.

The description of the constituent elements in the present invention described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

In the notation of the group (atomic group) in the present specification, the notation that does not describe substituted or unsubstituted includes not only having no substituent but also having a substituent. For example, the term "alkyl group" includes not only an alkyl group not having a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams in exposure unless otherwise specified. In addition, as the light used for exposure, in general, a bright ray spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV rays), X-rays, actinic rays such as electron rays, or radiation can be mentioned.

In the present specification, the numerical range indicated by using "~" means a range including a numerical value described before and after "~" as a lower limit value and an upper limit value.

In the present specification, "(meth)acrylate" represents both or any one of "acrylate" and "methacrylate", and "(meth)allyl" refers to "allyl" and "metalyl". Represents both or any one, (meth)acrylic" represents both or any one of "acrylic" and "methacryl", and "(meth)acryloyl" represents "acryloyl" and "methacrylic" Both or any one of "acryloyl" is shown.

In the present specification, the term "step" is included in this term not only as an independent step, but also in the case where the desired action of the step is achieved even if it cannot be clearly distinguished from other steps.

In this specification, the solid content concentration is a mass percentage of the components other than the solvent with respect to the total mass of the composition. In addition, the solid content concentration refers to the concentration at 25°C unless otherwise specified.

In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values by 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, guard column HZ-L and TSKgel Super HZM-M using HLC-8220 (manufactured by Tosoh Corporation) as columns. , TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, the eluent is measured using THF (tetrahydrofuran). In addition, the detection is assumed to be using a UV ray (ultraviolet) wavelength 254 nm detector unless otherwise specified.

[Method of manufacturing laminate]

The method for producing a laminate of the present invention includes a photosensitive resin composition layer forming step in which a photosensitive resin composition is applied to a substrate to form a layer,

An exposure process of exposing the photosensitive resin composition layer applied to the substrate, and

A developing treatment step of performing a development treatment on the exposed photosensitive resin composition layer, and

A curing step of curing the photosensitive resin composition layer after image development.

Including performing a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer after the curing step by vapor phase film formation in the above order,

The temperature of the photosensitive resin composition layer after the curing step when forming the metal layer is less than the glass transition temperature of the photosensitive resin composition layer after the curing step.

With the above configuration, it is possible to suppress interlayer peeling when the substrate, the cured film, and the metal layer are laminated.

When a metal layer is formed on the surface of a cured film on a substrate (the cured film refers to a photosensitive resin composition layer after the curing process) by vapor phase film formation such as sputtering, the substrate (and cured film) is usually used to control the film quality of the metal layer. ) To heat. Conventionally, it has been estimated that when a metal layer is formed by a sputtering method at a high temperature, metal atoms can be injected into a cured film, and as a result, the occurrence of delamination can be suppressed.

In fact, the present inventors analyzed the cross-section of a laminate in which a metal layer was formed on the surface of a cured film using a sputtering method using a transmission electron microscope (TEM), etc., as a result of analyzing the metal layer using a sputtering method at a high temperature. When is formed, it can be seen that the phenomenon that the metal enters the surface of the cured film (penetration) occurs. However, it was found that when the metal layer was formed by sputtering at a high temperature, interlayer peeling occurred when the substrate, the cured film, and the metal layer were laminated.

On the other hand, a phenomenon in which metal enters the surface of the cured film by forming a metal layer by vapor phase film formation such as sputtering so that the temperature of the photosensitive resin composition layer after the curing process (the temperature of the surface of the cured film) is suppressed below the glass transition temperature. It was found that no delamination occurs when the substrate, the cured film, and the metal layer are laminated. The glass transition temperature is hereinafter also referred to as Tg (glass transition temperature).

Hereinafter, details of a preferred embodiment of the present invention will be described.

<Filtration process>

The manufacturing method of the layered product of the present invention may include a step of filtering the photosensitive resin composition before applying the photosensitive resin composition to the substrate. It is preferable to perform filtration using a filter. As the filter pore diameter, 1 μm or less is preferable, 0.5 μm or less is more preferable, and 0.1 μm or less is still more preferable. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. You may use the filter previously washed with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel to be used. When using a plurality of types of filters, filters having different pore diameters and/or materials may be used in combination. Moreover, you may filter multiple times using each kind of material, and the process of filtering multiple times may be a circulation filtration process. Further, pressure filtration may be performed, and the pressure applied in the case of pressure filtration is preferably 0.05 MPa or more and 0.3 MPa or less.

In addition to filtration using a filter, filtration using an adsorbent may be performed to remove impurities, or filtration may be performed using a combination of filter filtration and an adsorbent. As the adsorbent, a known adsorbent may be used. For example, an inorganic adsorbent such as silica gel and zeolite, or an organic adsorbent such as activated carbon may be used.

<Photosensitive resin composition layer formation process>

The method for producing a laminate of the present invention includes a photosensitive resin composition layer forming step in which a photosensitive resin composition is applied to a substrate to form a layer shape.

As a means of applying the photosensitive resin composition to a substrate, application is preferable.

Specifically, as a means to be applied, 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 spray coating method, a spin coating method, a slit coating method, and The ink jet method and the like are illustrated. From the viewpoint of the uniformity of the thickness of the photosensitive resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an ink jet method are more preferable. A desired photosensitive resin composition layer can be obtained by adjusting an appropriate solid content concentration and application conditions according to the means to be applied. In addition, a coating method can be appropriately selected depending on the shape of the substrate, and if it is a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and if a rectangular substrate is a slit coating method, a spray coating method, an inkjet method And the like are preferred. In the case of the spin coating method, it can be applied for about 10 seconds to 1 minute at a rotation speed of, for example, 500 to 2000 rpm (revolutions per minute).

The thickness of the photosensitive resin composition layer (cured film after the curing step) is preferably applied so that it may be 0.1 to 100 μm after exposure, more preferably 1 to 50 μm. Moreover, as shown in FIG. 2, the thickness of the formed photosensitive resin composition layer does not necessarily need to be uniform. In particular, when the photosensitive resin composition layer is provided on the uneven surface, as shown in Fig. 2, cured films having different thicknesses will be obtained. In particular, when a plurality of layers of cured films are laminated, a deep concave portion may be formed as a concave portion, but the present invention has a high technical value in that it is possible to more effectively suppress delamination between layers for such a configuration. When the laminate has a cured film having a different thickness, it is preferable that the thickness of the cured film at the thinnest portion is the aforementioned thickness.

<<substrate>>

The type of substrate can be appropriately determined depending on the application, but semiconductor manufacturing substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, Ni , Metal substrates such as Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, plasma display panels (PDP) electrode plates, etc. are not particularly restricted. In the present invention, a semiconductor fabrication substrate is particularly preferred, and silicon is more preferred.

Moreover, when forming a photosensitive resin composition layer on the surface of a cured film or a surface of a metal layer, a cured film or a metal layer may be used as a board|substrate.

<<Photosensitive resin composition>>

Hereinafter, details of the photosensitive resin composition used in the present invention will be described.

In the method for producing a layered product of the present invention, it is preferable that the photosensitive resin composition contains a compound that forms a crosslinked structure by exposure, more preferably for negative development, and a crosslinked structure is formed by exposure to an organic solvent. It is particularly preferable that the solubility in water decreases, and it is most preferable that it is a negative photosensitive resin developed with an organic solvent.

First, components that may be included in the photosensitive resin composition used in the present invention are described. The photosensitive resin composition may contain components other than these, and also these components are not essential.

<<<resin>>>

The photosensitive resin composition used by this invention contains resin.

In the photosensitive resin composition used in the present invention, the resin is not particularly limited, and a known resin can be used. It is preferable that the resin is a high heat-resistant resin.

It is preferable that the photosensitive resin composition used by this invention contains at least 1 type of resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole. In the method for producing a laminate of the present invention, it is more preferable that the photosensitive resin composition contains a polyimide precursor or a polybenzoxazole precursor, and further preferably a polyimide precursor.

The photosensitive resin composition used in the present invention may contain only one type of polyimide precursor, polyimide, polybenzoxazole precursor, and polybenzoxazole, and may contain two or more types. Moreover, it is resin of the same type, such as two types of polyimide precursors, and may contain two or more types of resins with different structures.

In the photosensitive resin composition used in the present invention, the content of the resin is preferably 10 to 99% by mass, more preferably 50 to 98% by mass, and more preferably 70 to 96% by mass of the total solid content of the photosensitive resin composition. Do.

It is preferable that the resin further contains a polymerizable group.

Moreover, it is preferable that a photosensitive resin composition contains a polymeric compound. With such a configuration, a three-dimensional network is formed in the exposed portion, resulting in a strong crosslinked film, and the photosensitive resin composition layer (cured film) is not damaged by the surface activation treatment described later, and is cured by the surface activation treatment. The adhesion between the film and the metal layer or the adhesion between the cured film is more effectively improved.

In addition, it is preferable that the resin contains a partial structure represented by -Ar-L-Ar-. However, Ar is each independently an aromatic group, L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ -or- NHCO-, and a group consisting of a combination of two or more of the above. By setting it as such a structure, the photosensitive resin composition layer (cured film) becomes a flexible structure, and the effect of suppressing the occurrence of interlayer peeling is exhibited more effectively. Ar is preferably a phenylene group, and L is more preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO ₂ -. The aliphatic hydrocarbon group here is preferably an alkylene group.

(Polyimide precursor)

The polyimide precursor is not specifically determined with respect to its kind and the like, and it is preferable to include a repeating unit represented by the following formula (2).

Equation (2)

[Formula 1]

In formula (2), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ are, Each independently represents a hydrogen atom or a monovalent organic group.

As for A ¹ and A ² in Formula (2), an oxygen atom or NH is preferable, and an oxygen atom is more preferable.

R ¹¹¹ in formula (2) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, and 6 carbon atoms A group consisting of an aromatic group of to 20 or a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. As a particularly preferred embodiment, a group represented by -Ar-L-Ar- in R ¹¹¹ in formula (2) is illustrated. However, Ar is each independently an aromatic group, L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ -or- NHCO-, and a group consisting of a combination of two or more of the above. These preferable ranges are as described above.

It is preferable that R ¹¹¹ in formula (2) is derived from diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, and two or more types may be used.

Specifically, it is preferable that it is a diamine containing a group consisting of a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof. It is more preferable that it is a diamine containing a group consisting of 6-20 aromatic groups. Examples of the aromatic group include the following aromatic groups.

[Formula 2]

Among the aromatic groups, A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NHCO- and a group selected from a combination thereof is 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 -is more preferably a group selected from -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) ₂ It is more preferable that it is a divalent group selected from the group consisting of -.

As diamine, specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohex three; 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 Phosphorus and isophoronediamine; Meta and paraphenylenediamine, diaminotoluene, 4,4'- and 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether , 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenylsulfone, 4,4'- and 3,3'-diaminodi Phenylsulfide, 4,4'- and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'- Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexa Fluoropropane, 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'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-amino Phenoxy)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'-di Methyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2 -Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobi Phenyl, 3,3',4,4'-tetraaminodiphenylether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'- Diamino bipe Nyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4 ,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetra Methyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-di Aminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, ester of diaminobenzoic acid, 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) Si)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, parabis(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-tri Fluoromethylphenoxy)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-tri) Fluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'- At least one dia selected from bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine and 4,4'''-diaminoquaterphenyl Min can be mentioned.

Moreover, diamines (DA-1) to (DA-18) shown below are also preferable.

[Formula 3]

[Formula 4]

Moreover, a diamine which has at least 2 or more alkylene glycol units in a main chain is also mentioned as a preferable example. Preferably, it is a diamine containing two or more of ethylene glycol chain, propylene glycol chain, or both, in one molecule, and more preferably a diamine not containing an aromatic ring. As a specific example, Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, Jeffamine (registered trademark) EDR -148, Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (above brand name, manufactured by HUNTSMAN), 1-(2-(2-(2-aminopropoxy)) )Ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, etc. are mentioned, but limited to these It doesn't work.

Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, Jeffamine (registered trademark) EDR-148, The structure of Jeffamine (registered trademark) EDR-176 is shown below.

[Formula 5]

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

It is preferable that R ¹¹¹ in Formula (2) is represented by -Ar-L-Ar- from the viewpoint of flexibility of the obtained cured film. However, Ar is each independently an aromatic group, L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ -or- NHCO-, and a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is more preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO ₂ -. The aliphatic hydrocarbon group here is preferably an alkylene group.

It is preferable that R ¹¹¹ in Formula (2) is a divalent organic group represented by following Formula (51) or Formula (61) from a viewpoint of i-ray transmittance. In particular, it is more preferable that it is a divalent organic group represented by Formula (61) from the viewpoint of i-ray transmittance and availability.

Equation (51)

[Formula 6]

In formula (51), R ¹⁰ to R ¹⁷ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R ¹⁰ to R ¹⁷ is a fluorine atom, a methyl group, or a trifluoromethyl group.

Examples of the monovalent organic group of R ¹⁰ to R ¹⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), etc. I can.

Equation (61)

[Formula 7]

In formula (61), R ¹⁸ and R ¹⁹ are each independently a fluorine atom or a trifluoromethyl group.

Examples of the diamine compound giving the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. are mentioned. These may use 1 type, or may be used combining two or more types.

R ¹¹⁵ in Formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or (6) is more preferable.

Equation (5)

[Formula 8]

In formula (5), R ¹¹² is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ -, -NHCO- And, a group selected from a combination thereof is preferably a group selected from a single bond, 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, -CH ₂ -, -C (CF ₃ ) ₂ -, -C (CH ₃ ) ₂ -, -O-, -CO-, -S- and -SO ₂ -selected from the group consisting of Divalent groups are more preferred.

Equation (6)

[Formula 9]

R ¹¹⁵ in formula (2) specifically includes a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, and two or more types may be used.

It is preferable that the tetracarboxylic dianhydride is represented by the following formula (O).

Equation (O)

[Formula 10]

In formula (O), R ¹¹⁵ represents a tetravalent organic group. A preferable range of the R ¹¹⁵ is R ^115, and accept in the formula (2) are also the same preferable range.

Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3 ,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic acid Dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzo Phenonetetracarboxylic 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)hexafluoro Propane 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-naphthalenetetra Carboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl) ) At least one type selected from ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and these alkyl having 1 to 6 carbon atoms and/or alkoxy derivatives having 1 to 6 carbon atoms is illustrated.

Moreover, tetracarboxylic dianhydride (DAA-1)-(DAA-5) shown below are also mentioned as a preferable example.

[Formula 11]

It is also preferable to have a hydroxy group in at least one of R ¹¹¹ and R ¹¹⁵ in formula (2). More specifically, as R ¹¹¹ , a residue of a bisaminophenol derivative is exemplified.

R ¹¹³ and R ¹¹⁴ in formula (2) each independently represent a hydrogen atom or a monovalent organic group.

It is preferable that at least one of R ¹¹³ and R ¹¹⁴ in the formula (2) contains a polymerizable group, and both preferably contain a polymerizable group. The polymerizable group is a group capable of crosslinking reaction by action such as heat and radicals. As the polymerizable group, a photoradical polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a block isocyanate group, a methylol group, and an amino group. I can. As the radical polymerizable group that the polyimide precursor has, a group having an ethylenically unsaturated bond is preferable.

Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a group represented by the following formula (III).

[Formula 12]

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 are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group , A dodecamethylene group, and -CH ₂ CH(OH)CH ₂ -are mentioned, and an ethylene group, a propylene group, a trimethylene group, and -CH ₂ CH(OH)CH ₂ -are more preferable.

Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.

R ¹¹³ or R ¹¹⁴ in formula (2) may be a monovalent organic group other than a polymerizable group.

From the viewpoint of solubility in an organic solvent, it is preferable that R ¹¹³ or R ¹¹⁴ in the formula (2) is a monovalent organic group. As a monovalent organic group, it is preferable to contain a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group. As the monovalent organic group, an aromatic group having 1, 2 or 3 (preferably 1) acidic groups bonded to the carbon constituting the aryl group, and 1, 2 or 3 bonded to the carbon constituting the aryl group Aralkyl groups having four (preferably one) acidic groups are particularly preferred. Specifically, an aromatic group having an acidic group and having 6 to 20 carbon atoms and an aralkyl group having an acidic group and having 7 to 25 carbon atoms are mentioned. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group are mentioned. The acidic group is preferably a hydroxy group.

It is more particularly preferable that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.

The number of carbon atoms of the alkyl group represented by R ¹¹³ or R ¹¹⁴ in Formula (2) is preferably 1 to 30. As a linear or branched alkyl group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, an octadecyl group, iso A propyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a 1-ethylpentyl group, and a 2-ethylhexyl group are mentioned.

The cyclic alkyl group represented by R ¹¹³ or R ¹¹⁴ in formula (2) may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. As a monocyclic cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are mentioned, for example. Examples of the polycyclic cyclic alkyl group include adamantyl group, norbornyl group, bonyl group, campenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camporoyl group, dicyclohexyl group and pinenyl group. Can be lifted. Among them, a cyclohexyl group is most preferred from the viewpoint of compatibility with high sensitivity. Moreover, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group mentioned later is preferable.

As the aromatic group represented by R ¹¹³ or R ¹¹⁴ in formula (2), specifically, a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring , Pentacene ring, acenaphthene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thi Azole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizin ring, quinoline ring, phthalazine ring, naphthii Lidin ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, cyanthrene ring, chromaen ring, xanthene ring, phenoxacyin ring, phenothiazine ring Or a phenazine ring. The benzene ring is most preferred.

When R ¹¹³ in formula (2) is a hydrogen atom, or when R ¹¹⁴ in formula (2) is a hydrogen atom, the polyimide precursor forms a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. You can do it. Examples of the tertiary amine compound having such an ethylenically unsaturated bond include N,N-dimethylaminopropyl methacrylate.

Moreover, it is also preferable that a polyimide precursor has a fluorine atom in a structural unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

Further, for the purpose of improving the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with a polyimide precursor. Specifically, as the diamine component for introducing an aliphatic group having a siloxane structure, bis(3-aminopropyl)tetramethyldisiloxane, bis(paraaminophenyl)octamethylpentasiloxane, and the like can be mentioned.

It is preferable that the repeating unit represented by formula (2) is a repeating unit represented by following formula (2-A). That is, it is preferable that at least one type of polyimide precursor is a precursor having a repeating unit represented by formula (2-A). By setting it as such a structure, it becomes possible to further expand the width of the exposure latitude.

Equation (2-A)

[Formula 13]

In formula (2-A), A ¹ and A ² represent an oxygen atom, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, and R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom Or a monovalent organic group, at least one of R ¹¹³ and R ¹¹⁴ is a group containing a polymerizable group, and is preferably a polymerizable group.

Formula ^{(2-A) A 1,} A 2, R in a ^111, R ¹¹³ and R ¹¹⁴ are each independently formula ^{(2) A 1, A 2} , R 111, R 113 and R ¹¹⁴ in the It is synonymous with and the preferable range is also the same.

R ¹¹² in the formula (2-A) is, and R ¹¹² and consent of the formula (5), are also the same preferable range.

In a polyimide precursor, although one type may be sufficient as the repeating unit represented by Formula (2), it may be two or more types. Moreover, the polyimide precursor may contain the structural isomer of a repeating unit represented by Formula (2). Moreover, the polyimide precursor may also contain other types of repeating units in addition to the repeating units represented by the above formula (2).

As an embodiment of the polyimide precursor in the present invention. A polyimide precursor in which 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more of the total repeating units is a repeating unit represented by formula (2), is exemplified.

It is preferable that a polyimide precursor is obtained by making a dicarboxylic acid or a dicarboxylic acid derivative and a diamine react. It is more preferable that a dicarboxylic acid or a dicarboxylic acid derivative is halogenated using a halogenating agent and then reacted with a diamine. The polyimide precursor is, for example, a method of reacting a tetracarboxylic dianhydride and a diamine compound (partly substituted with a monoamine end sealant) at low temperature, and a tetracarboxylic dianhydride (partly an acid anhydride or monoacid chloride compound) at low temperature. Alternatively, a method of reacting a diamine compound with a mono-active ester compound (substituting with an end sealant), obtaining a diester with a tetracarboxylic dianhydride and an alcohol, and then condensing with a diamine (substituting a part with a monoamine end-sealing agent) A method of reacting in the presence of an agent, obtaining a diester with tetracarboxylic dianhydride and alcohol, and then acid chloride of the remaining dicarboxylic acid, and reacting with diamine (partly substituted with a monoamine end sealant) It is obtained using a method such as.

In the manufacturing method of a polyimide precursor, it is preferable to use an organic solvent at the time of reaction. One type of organic solvent may be sufficient, and two or more types may be sufficient as it.

As the organic solvent, although it can be appropriately determined depending on the raw material, pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone are exemplified.

In the preparation of the polyimide precursor, in order to further improve storage stability, it is preferable to seal with an end sealant such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a mono active ester compound. Among these, it is more preferable to use a monoamine, and as preferable compounds of the monoamine, aniline, 2-ethanylaniline, 3-ethanylaniline, 4-ethanylaniline, and 5-amino-8-hydroxy Quinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-amino Naphthalene, 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-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol , 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more types of these may be used, or a plurality of different terminal groups may be introduced by reacting a plurality of end sealing agents.

At the time of production of the polyimide precursor, a step of depositing a solid may be included. Specifically, the polyimide precursor in the reaction solution is precipitated in water, and a polyimide precursor such as tetrahydrofuran is dissolved in a soluble solvent, whereby solid precipitation can be achieved.

Thereafter, the polyimide precursor is dried to obtain a powdery polyimide precursor.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18000 to 30000, more preferably 20000 to 27000, further preferably 22000 to 25000. Moreover, the number average molecular weight (Mn) becomes like this. Preferably it is 7200-14000, More preferably, it is 8000-12000, More preferably, it is 9200-11200.

The degree of dispersion of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and even more preferably 2.8 or more. Although the upper limit of the degree of dispersion of the polyimide precursor is not particularly determined, for example, 4.5 or less is preferable, 4.0 or less is more preferable, 3.8 or less is more preferable, 3.2 or less is even more preferable, and 3.1 or less is even more. It is more preferable, 3.0 or less is especially preferable, and 2.95 or less is most preferable.

(Polyimide)

The polyimide is not particularly limited as long as it is a polymer compound having an imide ring. The polyimide is preferably a compound represented by the following formula (4), and more preferably a compound having a polymerizable group as the compound represented by the formula (4).

Equation (4)

[Formula 14]

In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group.

In the case of having a polymerizable group, at least one of R ¹³¹ and R ¹³² may have a polymerizable group, and even if it has a polymerizable group at the terminal of the polyimide as shown in the following formula (4-1) or formula (4-2) do.

Equation (4-1)

[Formula 15]

In formula (4-1), R ¹³³ is a polymerizable group, and other groups have the same definition as formula (4).

Equation (4-2)

[Formula 16]

In formula (4-2), at least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group, the other is an organic group, and the other group has the same definition as formula (4).

The polymerizable group preferably contained in the polyimide is the same as the polymerizable group used as the polymerizable group which may be contained in R ¹¹³ and R ¹¹⁴ in the formula (2) in the polyimide precursor.

R ¹³¹ in formula (4) represents a divalent organic group. As a divalent organic group, a divalent organic group similar to R ¹¹¹ in Formula (2) is illustrated, and a preferable range is also the same.

Further, as the R ^131, there may be mentioned a diamine residue remaining after removing an amino group of diamine. Examples of the diamine include aliphatic, cyclic aliphatic, or aromatic diamine. As a specific example, the example of R ¹¹¹ in Formula (2) of a polyimide precursor is mentioned.

R ¹³¹ in formula (4) is preferably a diamine residue having at least two or more alkylene glycol units in the main chain from the viewpoint of more effectively suppressing the occurrence of warpage during firing. More preferably, it is a diamine residue containing two or more of ethylene glycol chain, propylene glycol chain, or both, in one molecule, and more preferably a diamine residue not containing an aromatic ring.

As diamine containing two or more of ethylene glycol chain and propylene glycol chain in one molecule, or both, specific examples similar to diamines capable of inducing R ¹¹¹ in formula (2), etc. Although can be mentioned, it is not limited to these.

R ¹³² in formula (4) represents a tetravalent organic group. Examples of the tetravalent organic group represented by R ¹³² are the same as those of R ¹¹⁵ in formula (2), and the preferred range is also the same.

For example, as R ¹¹⁵ in formula (2), four bonds of a tetravalent organic group of the following structure exemplified are bonded to four -C(=O)- moieties in the formula (4), It forms a condensed ring.

[Formula 17]

Examples of R ¹³² in formula (4) include a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic dianhydride. As a specific example, the example of R ¹¹⁵ in Formula (2) of a polyimide precursor is mentioned. From the viewpoint of the strength of the cured film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferable that at least one of R ¹³¹ and R ¹³² in formula (4) has a hydroxy group. More specifically, as R ¹³¹ in formula (4), 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, The above (DA-1) to (DA-18) are mentioned as a preferable example. As R ¹³² in formula (4), the above (DAA-1) to (DAA-5) are mentioned as a preferable example.

Moreover, it is also preferable that a polyimide has a fluorine atom in a structural unit. The fluorine atom content in the polyimide is preferably 10% by mass or more, and preferably 20% by mass or less.

Further, for the purpose of improving the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with polyimide. Specifically, examples of the diamine component for introducing an aliphatic group having a siloxane structure include bis(3-aminopropyl)tetramethyldisiloxane, bis(paraaminophenyl)octamethylpentasiloxane, and the like.

Further, in order to improve the storage stability of the photosensitive resin composition, it is preferable to seal the end of the main chain of the polyimide with an end sealant such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a mono active ester compound. Among these, it is more preferable to use a monoamine. Preferred examples of monoamines include aniline, 2-ethynylaniline, 3-ethanylaniline, 4-ethanylaniline, 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-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. are mentioned. Two or more types of these may be used, or a plurality of different terminal groups may be introduced by reacting a plurality of end sealing agents.

As for the polyimide, it is preferable that the imidation ratio is 85% or more, and it is more preferable that it is 90% or more. When the imidation ratio is 85% or more, film shrinkage due to ring closure that occurs when imidization is performed by heating is small, and the occurrence of warpage of the substrate can be suppressed.

In addition to the repeating unit represented by the above formula (4) in which all of the polyimide is one type of R ¹³¹ or R ¹³² , the polyimide may contain two or more different types of repeating units of R ¹³¹ or R ¹³² . Moreover, in addition to the repeating unit represented by the said formula (4), the polyimide may also contain other types of repeating units.

After synthesizing a polyimide precursor, a polyimide may be produced by heating to cyclize, or a polyimide may be synthesized directly.

In polyimide, a method of obtaining a polyimide precursor and completely imidizing it using a known imidization reaction method, or a method of stopping the imidation reaction in the middle and introducing a partial imide structure, furthermore completely imidization By blending one polymer and the polyimide precursor, it can be synthesized using a method of introducing a partial imide structure.

As a commercial product of polyimide, Durimide (registered trademark) 284 (manufactured by Fujifilm) and Matrimide5218 (manufactured by HUNTSMAN) are illustrated.

5,000 to 70,000 are preferable, as for the weight average molecular weight (Mw) of a polyimide, 8,000 to 50,000 are more preferable, and 10,000 to 30,000 are especially preferable. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the film after curing can be improved. In order to obtain a cured film excellent in mechanical properties, the weight average molecular weight is more preferably 20,000 or more. Moreover, when it contains two or more types of polyimide, it is preferable that the weight average molecular weight of at least 1 type of polyimide is the said range.

(Polybenzoxazole precursor)

The polybenzoxazole precursor is not specifically determined with respect to the kind or the like, and it is preferable to include a repeating unit represented by the following formula (3).

Equation (3)

[Formula 18]

In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

R ¹²³ and R ¹²⁴ in formula (3) are the same as R ¹¹³ in formula (2), respectively, and the preferred ranges are also the same. That is, it is preferable that at least one of R ¹²³ and R ¹²⁴ in formula (3) is a polymerizable group.

R ¹²¹ in formula (3) represents a divalent organic group. The divalent organic group represented by R ¹²¹ is preferably a group containing at least one of an aliphatic group and an aromatic group. As the aliphatic group, a linear aliphatic group is preferable. R ¹²¹ is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, and two or more types may be used.

As the dicarboxylic acid, a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid containing an aromatic group are preferable, and a dicarboxylic acid containing an aromatic group is more preferable.

As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferable, and a dicarboxylic acid consisting of a linear or branched (preferably linear) aliphatic group and two COOH is more preferable. Do. The number of carbon atoms of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, more preferably 3 to 20, and even more preferably 4 to 15 And it is particularly preferably 5 to 10. It is preferable that the linear aliphatic group is an alkylene group.

As the dicarboxylic acid containing a linear aliphatic group, malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2 -Dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2, 2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azeric acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid , Tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanoic acid, octadecanedioic acid, nonadecanoic acid, eicosane diacid, heneichoic acid diacid, docoic acid diacid, trichoic acid diacid, tetracoic acid diacid, pentacoic acid diacid, Hexacoic acid diacid, heptaconic acid diacid, octacoic acid diacid, nonaconic acid diacid, triaconic acid, hentriacontanic acid, dotriacontanic acid, diglycholic acid, and dicarboxylic acid represented by the following formula. have.

[Formula 19]

(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

As the dicarboxylic acid containing an aromatic group, a dicarboxylic acid having the following aromatic groups is preferable, and a dicarboxylic acid consisting of only the following aromatic groups and two COOH is more preferable.

[Formula 20]

Among the above aromatic groups, A is -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) _It represents a divalent group selected from the group consisting of ₂ -.

As specific examples of the dicarboxylic acid containing an aromatic group, 4,4'-carbonyl dibenzoic acid, 4,4'-dicarboxydiphenyl ether and terephthalic acid are preferable.

R ¹²² in formula (3) represents a tetravalent organic group. Examples of the tetravalent organic group represented by R ¹²² are the same as those of R ¹¹⁵ in the formula (2), and the preferred range is also the same.

It is preferable that R ¹²² in formula (3) is also a group derived from a bisaminophenol derivative. Examples of groups derived from bisaminophenol derivatives include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis-(3-amino-4-hydroxyl) Roxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2, 2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3- Hydroxyphenyl) propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'- Diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydro Hydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. are mentioned. These bisaminophenols may be used alone or in combination.

Among the bisaminophenol derivatives, bisaminophenol derivatives having the following aromatic groups are preferred.

[Formula 21]

In the above formula, X ₁ represents -O-, -S-, -C(CF ₃ ) ₂ -, -CH ₂ -, -SO ₂ -, -NHCO-.

Equation (A-s)

[Formula 22]

In formula (As), R ₁ is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, a single bond, or the following formula (A- It is an organic group selected from the group of sc).

In formula (As), R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.

In formula (As), R ₃ is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.

Equation (A-sc)

[Formula 23]

(In formula (A-sc), * represents bonded to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (A-s).)

In the above formula (As), it is thought that having a substituent in the ortho position of the phenolic hydroxy group, that is, also in R ₃ , makes the distance between the carbonyl carbon of the amide bond and the hydroxy group closer, and when cured at low temperature It is particularly preferable because the effect of becoming a high ring rate becomes higher.

In addition, in the formula (As), it is preferable that R ₂ is an alkyl group and R ₃ is an alkyl group because the effect of high transparency to i-line and a high cyclization rate can be maintained when cured at low temperature.

In addition, in the formula (As), it is more preferable that R ₁ is alkylene or substituted alkylene. Specific examples of the alkylene and substituted alkylene represented by R ₁ include -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -CH(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ )(CH ₂ CH ₃ )-, -CH(CH ₂ CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -CH(CH(CH ₃ ) ₂ )-, -C(CH ₃ )(CH(CH ₃ ) ₂ )-, -CH(CH ₂ CH ₂ CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH(CH ₂ CH(CH ₃ ) ₂ )-, -C(CH ₃ )(CH ₂ CH(CH ₃ ) ₂ )-, -CH(CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, etc., but among them -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) _2- A, it is more preferable from the viewpoint of being able to obtain a polybenzoxazole precursor having sufficient solubility in a solvent and excellent in balance while maintaining the effect of high transparency to i-line and a high cyclization rate when cured at low temperature.

As a method for producing a bisaminophenol derivative represented by the above formula (As), for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP2013-256506A can be referred to, and these The contents are incorporated herein by reference.

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs 0070 to 0080 of JP2013-256506A, and the contents of these are incorporated herein. Of course, it is not limited to these.

The polybenzoxazole precursor may also contain other types of repeating units in addition to the repeating units represented by the above formula (3).

In terms of suppressing the occurrence of warpage of the substrate due to cyclization of the polybenzoxazole precursor, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit. .

[Formula 24]

In formula (SL), Z has a structure a and a structure b, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ^2s is a hydrocarbon group having 1 to 10 carbon atoms, R ^3s , R At least one of ^4s , R ^5s and R ^6s is an aromatic group, and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. The mole% of the Z part is 5 to 95 mole% for the a structure, 95 to 5 mole% for the b structure, and the sum of the a structure and the b structure is 100 mole%.

In formula (SL), preferable Z is that R ^5s and R ^6s in the b structure are a phenyl group.

Moreover, it is preferable that it is 400-4,000, and, as for the molecular weight of the diamine residue represented by Formula (SL), 500-3,000 are more preferable. By setting the molecular weight of the diamine moiety represented by the formula (SL) within the above range, the elastic modulus after dehydration and cyclization of the polybenzoxazole precursor is lowered more effectively, and the effect of suppressing the warpage of the substrate and the effect of improving the solvent solubility are compatible. can do.

When a diamine residue represented by formula (SL) is included as another type of repeating unit, it is also preferable to include a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride as a repeating unit. As an example of such a tetracarboxylic acid residue, the example of R ¹¹⁵ in Formula (2) is mentioned.

The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, when used for a composition described later, preferably 18000 to 30000, more preferably 20000 to 29000, and still more preferably 22000 to 28000. Moreover, the number average molecular weight (Mn) becomes like this. Preferably it is 7200-14000, More preferably, it is 8000-12000, More preferably, it is 9200-11200.

The dispersion degree of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and still more preferably 1.6 or more. The upper limit of the dispersibility of the polybenzoxazole precursor is not particularly determined, but for example, 2.6 or less is preferable, 2.5 or less is more preferable, 2.4 or less is more preferable, 2.3 or less is even more preferable, and 2.2 or less is It is particularly preferred.

(Polybenzoxazole)

The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring. The polybenzoxazole is preferably a compound represented by the following formula (X), and more preferably a compound having a polymerizable group as a compound represented by the following formula (X).

[Formula 25]

In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group.

In the case of having a polymerizable group, at least one of R ¹³³ and R ¹³⁴ may have a polymerizable group, as shown in the following formula (X-1) or (X-2), You may have it.

Equation (X-1)

[Formula 26]

In formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a polymerizable group, the other is an organic group, and the other group is synonymous with formula (X).

Equation (X-2)

[Formula 27]

In formula (X-2), R ¹³⁷ is a polymerizable group, the other is a substituent, and the other group has the same definition as the formula (X).

The polymerizable group preferably in the polybenzoxazole is the same as the polymerizable group described in the polymerizable group possessed by the polyimide precursor.

R ¹³³ represents a divalent organic group. Examples of the divalent organic group include an aliphatic group or an aromatic group. As a specific example, the example of R ¹²¹ in Formula (3) of a polybenzoxazole precursor is mentioned. Moreover, its preferable example is the same as R ¹²¹ .

R ¹³⁴ represents a tetravalent organic group. As a tetravalent organic group, the example of R ¹²² in Formula (3) of a polybenzoxazole precursor is mentioned. Moreover, its preferable example is the same as R ¹²² .

For example, four bonds of a tetravalent organic group exemplified as R ¹²² combine with a nitrogen atom and an oxygen atom in the formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, the following structure is formed.

[Formula 28]

The polybenzoxazole is preferably 85% or more, and more preferably 90% or more. When the oxazole rate is 85% or more, film shrinkage caused by ring closure that occurs when oxazole is formed by heating is reduced, and the occurrence of warpage can be more effectively suppressed.

Polybenzoxazole is represented by the above formula (X) including two or more different types of R ¹³³ or R ¹³⁴ in addition to the repeating unit represented by the above formula (X) in which all are one type of R ¹³³ or R ¹³⁴ . You may include a repeating unit. Moreover, polybenzoxazole may also contain other types of repeating units in addition to the repeating unit represented by the above formula (X).

Polybenzoxazole is a polybenzoxazole precursor by reacting a compound selected from, for example, a bisaminophenol derivative, a dicarboxylic acid containing R ¹³³ , and a dicarboxylic acid dichloride and a dicarboxylic acid derivative of the dicarboxylic acid. It is obtained, and it is obtained by making it oxazole using a known oxazole reaction method.

Further, in the case of dicarboxylic acid, an active ester-type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield.

The weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the film after curing can be improved. In order to obtain a cured film excellent in mechanical properties, the weight average molecular weight is more preferably 20,000 or more. Moreover, when containing two or more types of polybenzoxazole, it is preferable that the weight average molecular weight of at least 1 type of polybenzoxazole is the said range.

(Other photosensitive resins)

It is possible to apply to the present invention as a photosensitive resin other than the above. As other photosensitive resins, epoxy resins, phenol resins, and benzocyclobutene resins can be used.

<<<polymerizable compound>>>

It is preferable that the resin has a polymerizable group or that the photosensitive resin composition contains a polymerizable compound. By setting it as such a structure, a cured film more excellent in heat resistance can be formed.

The polymerizable compound is a compound having a polymerizable group, and a known compound capable of crosslinking reaction by a radical, an acid, a base, or the like can be used. Examples of the polymerizable group include the polymerizable group described in the polyimide precursor. One type of polymerizable compound may be included, and two or more types may be included.

The polymerizable compound may be any of chemical forms such as a monomer, a prepolymer, an oligomer, or a mixture thereof and a multimer thereof.

In the present invention, the monomer type polymerizable compound (hereinafter, also referred to as a polymerizable monomer) is a compound different from the polymer compound. The polymerizable monomer is typically a low-molecular compound, preferably a low-molecular compound having a molecular weight of 2000 or less, more preferably a low-molecular compound having a molecular weight of 2000 or less, and more preferably a low-molecular compound having a molecular weight of 900 or less. In addition, the molecular weight of the polymerizable monomer is usually 100 or more.

Further, the oligomeric type polymerizable compound is typically a polymer having a relatively low molecular weight, and is preferably a polymer in which 10 to 100 polymerizable monomers are bonded. The weight average molecular weight of the oligomeric type polymerizable compound is preferably 2000 to 20,000, more preferably 2000 to 15000, and most preferably 2000 to 10000.

The number of functional groups of a polymerizable compound means the number of polymerizable groups in one molecule.

From the viewpoint of developability, the photosensitive resin composition preferably contains at least one bifunctional or higher polymerizable compound containing two or more polymerizable groups, and more preferably contains at least one trifunctional or higher polymerizable compound. .

Since the photosensitive resin composition can form a three-dimensional crosslinked structure and improve heat resistance, it is preferable to contain at least 1 type of a trifunctional or more polymerizable compound. Moreover, a mixture of a bifunctional or less polymerizable compound and a trifunctional or more polymerizable compound may be used.

Examples of the polymerizable compound include a compound containing a group having an ethylenically unsaturated bond; A compound having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group; Epoxy compounds; Oxetane compounds; Benzoxazine compounds are preferred.

(Compound containing a group having an ethylenically unsaturated bond)

As a 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.

Specific examples of the compound containing a group having an ethylenically unsaturated bond include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and these And polymers of, preferably, esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds, and multimers thereof. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group, or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, or a monofunctional or polyfunctional carboxylic acid Dehydration and condensation reactants with and the like are also suitably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group, monofunctional or polyfunctional alcohols, amines, thiols, and halogen groups or tosyloxy groups, etc. Substitution reaction products of unsaturated carboxylic acid esters or amides having a detachable substituent of, and monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. In addition, as another example, instead of the above unsaturated carboxylic acid, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid and vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, and the like.

As a specific example of the monomer of the polyhydric alcohol compound and the ester of an unsaturated carboxylic acid, as an acrylic acid ester, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol Lycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylol propane triacrylate, trimethylol propane tri(acryloyloxypropyl) ether, trimethylol Etain triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, di Pentaerythritol diacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri(acrylo) Monooxyethyl) isocyanurate, isocyanurate ethylene oxide-modified triacrylate, and polyester acrylate oligomers.

Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, and trimethylolethane. Trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate Rate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [para (3-methacrylic) Oxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis-[para(methacryloxyethoxy)phenyl]dimethylmethane, and the like.

As itaconic acid esters, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol Diitaconate, pentaerythritol diitaconate, sorbitol tetraitaconate, and the like.

Examples of the crotonic acid ester include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetra dicrotonate, and the like.

Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, and the like.

Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate, and the like.

Examples of other esters include, for example, Japanese Patent Publication No. 46-027926, Japanese Patent Publication No. 51-047334, and the aliphatic alcohol-based esters described in Japanese Patent Application Publication No. 57-196231, and Japanese Patent Application Laid-Open. Those having an aromatic skeleton described in Japanese Unexamined Patent Application Publication No. 59-005240, Japanese Unexamined Patent Publication No. 59-005241, and Japanese Unexamined Patent Publication No. Hei 2-226149, containing amino groups described in Japanese Unexamined Patent Publication No. It is also suitably used.

Moreover, as specific examples of the monomer of the polyvalent amine compound and the amide of an unsaturated carboxylic acid, methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, and 1,6-hexamethylenebis-methacryl Amide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like.

Examples of other preferable amide-based monomers include those having a cyclohexylene structure described in Japanese Laid-Open Patent Publication No. 54-021726.

Further, a urethane-based addition polymerizable monomer prepared by using an addition reaction of an isocyanate and a hydroxyl group is also suitable, and as such a specific example, it is described in Japanese Patent Publication No. 48-041708. Vinylurete containing two or more polymerizable vinyl groups in one molecule by adding a vinyl monomer containing a hydroxyl group represented by the following formula to a polyisocyanate compound having two or more isocyanate groups in one molecule And phosphorus compounds.

CH ₂ =C(R ⁴ )COOCH ₂ CH(R ⁵ )OH

(However, R ⁴ and R ⁵ represent H or CH ₃ .)

Further, urethane acrylates as described in Japanese Laid-Open Patent Publication No. 51-037193, Japanese Laid-Open Patent Publication No. Hei 2-032293, and Japanese Laid-open Patent Publication No. Hei 2-016765, or Japanese Laid-Open Patent Publication No. 58 Urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. -049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable.

Further, as the compound containing a group having an ethylenically unsaturated bond, the compounds described in paragraphs 0095 to 0108 of JP 2009-288705A can also be suitably used in the present invention.

Further, as the compound containing a group having an ethylenically unsaturated bond, a compound having a boiling point of 100°C or higher under normal pressure is also preferable. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl(meth)acrylate; Polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate )Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylol propane tri (acryloyloxypropyl) ether , Tri(acryloyloxyethyl) isocyanurate, added ethylene oxide or propylene oxide to polyfunctional alcohols such as glycerin or trimethylolethane, and then (meth)acrylated, Japanese Patent Publication No. 48 -041708, Japanese Laid-Open Patent Publication No. 50-006034, Japanese Laid-Open Patent Publication No. 51-037193, urethane (meth)acrylates as described in each publication, Japanese Laid-Open Patent Publication No. 48-064183 , Japanese Patent Publication No. 49-043191, Japanese Patent Publication No. 52-030490, polyester acrylates described in each publication, epoxy acrylates, which are reaction products of epoxy resin and (meth)acrylic acid, etc. And functional acrylates and methacrylates, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP 2008-292970 A are also suitable. Moreover, a polyfunctional (meth)acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having an ethylenically unsaturated group with a cyclic ether group such as glycidyl (meth)acrylate may be mentioned.

In addition, as a compound containing a group having another preferred ethylenically unsaturated bond, it has a fluorene ring described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, Japanese Patent No. 4362216, etc. , It is possible to use a compound having two or more groups having an ethylenically unsaturated bond, or a cardo resin.

In addition, as other examples, the specific unsaturated compounds described in Japanese Patent Laid-Open No. 46-043946, Japanese Patent Laid-Open No. Hei 1-040337, and Japanese Laid-Open Patent Publication No. Hei 1-040336, and Japanese Laid-Open Patent Publication No. Hei 2-025493 The vinylphosphonic acid compound etc. described in the issue are also mentioned. Moreover, in a predetermined case, the structure containing a perfluoroalkyl group described in Unexamined-Japanese-Patent No. 61-022048 is used suitably. Also, the Japanese Adhesives Association, vol. 20, No. 7, 300-308 pages (1984) as photopolymerizable monomers and oligomers can also be used.

In addition to the above, a compound containing a group having an ethylenically unsaturated bond represented by the following formulas (MO-1) to (MO-5) can also be suitably used. In addition, in the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

[Chemical Formula 29]

[Formula 30]

In each of the above formulas, n is an integer of 0 to 14, and m is an integer of 0 to 8. R and T present in a plurality of molecules may be the same or different, respectively.

In each of the polymerizable compounds represented by the formulas (MO-1) to (MO-5), at least one of a plurality of R is -OC(=O)CH=CH ₂ , or -OC(=O)C The group represented by (CH ₃ )=CH ₂ is shown.

As a specific example of a compound containing a group having an ethylenically unsaturated bond represented by the above formulas (MO-1) to (MO-5), the compounds described in paragraphs 0248 to 0251 of JP 2007-269779 Also in the invention, it can be used suitably.

Further, a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol as described in Japanese Patent Application Laid-Open No. Hei 10-062986 together with the specific examples thereof as formulas (1) and (2), and then (meth)acrylated Also, it can be used as a polymerizable compound.

In addition, the compounds described in paragraphs 0104 to 0131 of JP 2015-187211 A may also be employed, and the contents of these are incorporated in the present specification. In particular, the compound described in paragraphs 0128 to 0130 of the same publication is illustrated as a preferred embodiment.

As a compound containing a group having an ethylenically unsaturated bond, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product) ; Nippon Kayaku Co., Ltd. product), Dipentaerythritol penta (meth)acrylate (as a commercial product, KAYARAD D-310; Nippon Kayaku Co., Ltd. product), Dipentaerythritol hexa (meth)acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., and a structure in which these (meth)acryloyl groups are bonded via ethylene glycol and propylene glycol residues is preferable. These oligomer types can also be used.

Moreover, a pentaerythritol derivative and/or a dipentaerythritol derivative of the above formulas (MO-1) and (MO-2) are also mentioned as preferred examples.

Examples of commercially available polymeric compounds include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and SR-209, manufactured by Sartomer, which is a bifunctional methacrylate having four ethyleneoxy chains. , DPCA-60, a six-functional acrylate having six pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having three three isobutyleneoxy chains, and urethane oligomer UAS- 10, UAB-140 (manufactured by Sanyo Kokusaku Pulp), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shinnakamura Chemical Corporation), DPHA-40H ( Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (Nichiyu Co., Ltd.) Article), etc. are mentioned.

As a compound containing a group having an ethylenically unsaturated bond, Japanese Laid-Open Patent Publication No. 48-041708, Japanese Laid-Open Patent Publication No. 51-037193, Japanese Laid-open Patent Publication No. Hei 2-032293, and Japanese Laid-Open Patent Publication No. Hei 2-016765 Urethane acrylates as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, Japanese Patent Publication No. 62 Urethane compounds having an ethylene oxide skeleton described in No. -039418 are also suitable. In addition, as a polymerizable compound, the addition having an amino structure or a sulfide structure in a molecule described in JP-A-63-277653 A, JP-A-63-260909 A, and JP-A-105238 A Polymerizable monomers can also be used.

The compound containing a group having an ethylenically unsaturated bond may be a polyfunctional monomer having an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The polyfunctional monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a polyfunctional monomer obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of the aliphatic polyhydroxy compound to give an acid group is More preferable. Particularly preferably, in the polyfunctional monomer obtained by reacting a non-aromatic carboxylic anhydride to give an acid group to an unreacted hydroxy group of an aliphatic polyhydroxy compound, the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaeryth. It is litol. As a commercial item, M-510, M-520, etc. are mentioned as a polybasic acid-modified acrylic oligomer manufactured by Toa Kosei, for example.

One type of polyfunctional monomer having an acid group may be used alone, or two or more types may be mixed and used. Further, if necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination.

The preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH/g, particularly preferably 5 to 30 mgKOH/g. When the acid value of the polyfunctional monomer is within the above range, the production and handling properties are excellent, and furthermore, the developability is excellent. Moreover, the polymerizability is good.

The content of the compound containing a group having an ethylenically unsaturated bond is preferably 1 to 50% by mass with respect to the total solid content of the photosensitive resin composition from the viewpoint of good polymerization 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. One type of compound containing a group having an ethylenically unsaturated bond may be used alone, or two or more types may be mixed and used.

In addition, the mass ratio (resin/polymerizable compound) of the resin and the compound containing a group having an ethylenically unsaturated bond is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, and 90 /10-50/50 are most preferable. When the mass ratio of the resin and the compound containing a group having an ethylenically unsaturated bond is within the above range, an excellent cured film can be formed due to polymerization and heat resistance.

(Compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group)

As the compound having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group, a compound represented by the following formula (AM1) is preferable.

(AM1)

[Formula 31]

(In the formula, t represents an integer of 1 to 20, R ⁴ represents a t-valent organic group having 1 to 200 carbon atoms, and R ⁵ represents a group represented by the following formula (AM2) or the following formula (AM3).)

Equation (AM2) Equation (AM3)

[Formula 32]

(In the formula, R ⁶ represents a hydroxyl group or an organic group having 1 to 10 carbon atoms.)

It is preferable that the compound represented by formula (AM1) is 5 mass parts or more and 40 mass parts or less with respect to 100 mass parts of resin. More preferably, it is 10 mass parts or more and 35 mass parts or less. In addition, among all the polymerizable compounds, 10 mass% or more and 90 mass% or less of the compound represented by the following formula (AM4) is contained, and 10 mass% or more and 90 mass% or less of the compound represented by the following formula (AM5) are contained in the total thermal crosslinking agent. It is also desirable to do it.

(AM4)

[Formula 33]

(In the formula, R ⁴ represents a divalent organic group having 1 to 200 carbon atoms, and R ⁵ represents a group represented by the following formula (AM2) or the following formula (AM3).)

Expression (AM5)

[Formula 34]

(In the formula, u represents an integer of 3 to 8, R ⁴ represents a u-valent organic group having 1 to 200 carbon atoms, and R ⁵ represents a group represented by the following formula (AM2) or the following formula (AM3).)

Equation (AM2) Equation (AM3)

[Formula 35]

(In the formula, R ⁶ represents a hydroxyl group or an organic group having 1 to 10 carbon atoms.)

By setting it as this range, when the photosensitive resin composition layer is formed on the uneven|corrugated board|substrate, generation|occurrence|production of a crack becomes less. It is excellent in pattern processability, and may have high heat resistance such that the 5% mass reduction temperature is 350°C or higher, more preferably 380°C or higher. As a specific example of the compound represented by formula (AM4), 46DMOC, 46DMOEP (above, brand name, Asahi Yukizai Kogyo Co., Ltd. make), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML -PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above, brand name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 ( As mentioned above, the brand name, Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-buthylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacethoxymethyl-p-cresol, etc. are mentioned.

In addition, as a specific example of the compound represented by formula (AM5), TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP , HMOM-TPPHBA, HMOM-TPHAP (above, brand name, Honshu Chemical Industry Co., Ltd. product), TM-BIP-A (brand name, Asahi Yukizai High School Co., Ltd. product), NIKALAC MX-280, NIKALAC MX-270 , NIKALAC MW-100LM (above, brand name, manufactured by Sanwa Chemical Co., Ltd.) can be mentioned.

<<<Photopolymerization initiator>>>

The photosensitive resin composition may contain a photoinitiator. In particular, since the photosensitive resin composition contains a photo-radical polymerization initiator, the photosensitive resin composition is applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer, and then cured due to radicals occurs by irradiation with light. Solubility in can be reduced. For this reason, there is an advantage in that, for example, by exposing the photosensitive resin composition layer through a photomask having a pattern masking only the electrode portion, regions having different solubility can be conveniently manufactured according to the pattern of the electrode.

The photoinitiator is not particularly limited as long as it has the ability to initiate a polymerization reaction (crosslinking reaction) of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferable to have photosensitivity to light in the visible region from the ultraviolet region. Moreover, it may be an activator which generates an active radical by generating a certain action with a photo-excited sensitizer.

It is preferable that the photoinitiator contains at least one type of 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 the compound can be measured using a known method. Specifically, it is preferable to measure at a concentration of 0.01 g/L using, for example, an ultraviolet visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent.

As the photopolymerization initiator, known compounds can be used without limitation, but for example, halogenated hydrocarbon derivatives (e.g., those having a triazine skeleton, those having an oxadiazole skeleton, or those having a trihalomethyl group) Etc.), acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds , Hydroxyacetophenone, an azo compound, an azide compound, a metallocene compound, an organic boron compound, an iron arene complex, and the like.

As a halogenated hydrocarbon compound having a triazine skeleton, for example, Wakabayashi et al., Bull. Chem. Soc. Japan, 42, the compound described in 2924 (1969), the compound described in British Patent Publication No. 1388492, the compound described in Japanese Unexamined Patent Publication No. 53-133428, the compound described in German Patent Publication No. 3337024, FC Schaefer et al., J. Org. Chem.; 29, the compound described in 1527 (1964), the compound described in Japanese Laid-Open Patent Publication No. 62-058241, the compound described in Japanese Laid-Open Patent Publication No. Hei 5-281728, the compound described in Japanese Patent Application Laid-Open No. Hei 5-034920, United States The compounds described in Patent Publication No. 4212976, etc. are mentioned.

As the compound described in U.S. Patent Publication No. 4212976, for example, a compound having an oxadiazole skeleton (e.g., 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5-(4-chlorophenyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole, 2- Trichloromethyl-5-(2-naphthyl)-1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5 -(2-naphthyl)-1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(4- Chlorostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-methoxystyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl)-1,3,4-oxadiazole, 2-tribromomethyl-5-styryl-1,3,4-oxadiazole, etc.), etc. are mentioned.

In addition, as photopolymerization initiators other than the above, the compound described in paragraph 0086 of JP 2015-087611 A, JP-A 53-133428 A, JP-A 57-001819 A, 57-006096 A, and The compounds and the like described in U.S. Patent Publication No. 3615455 are illustrated, and the contents of these are incorporated herein.

As a ketone compound, the compound described in paragraph 0087 of Japanese Unexamined-Japanese-Patent No. 2015-087611 is illustrated, for example, and this content is incorporated in this specification.

In a commercial item, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

As a photoinitiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be used suitably. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 A and the acylphosphine oxide-based initiator described in JP-A-4225898 can also be used.

As the hydroxyacetophenone initiator, IRGACURE-184 (IRGACURE is a registered trademark), DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone initiator, the compound described in Japanese Patent Application Laid-Open No. 2009-191179 in which the maximum absorption wavelength is matched to a wavelength such as 365 nm or 405 nm can also be used.

Examples of the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. In addition, commercially available IRGACURE-819 and IRGACURE-TPO (brand names: all manufactured by BASF) can be used.

As a metallocene compound, IRGACURE-784 (made by BASF) etc. are illustrated.

As a photoinitiator, more preferably, an oxime compound is mentioned. By using an oxime compound, it becomes possible to improve the exposure latitude more effectively. The oxime ester compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a hot base generator.

As a specific example of the oxime compound, a compound described in JP 2001-233842 A, a compound described in JP 2000-080068 A, and a compound described in JP 2006-342166 A can be used.

Preferred oxime compounds include, for example, the following compounds, 3-benzoxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxy Minopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutane 2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

[Formula 36]

As an oxime compound, JCS Perkin II (1979) pp.1653-1660, JCS Perkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232 described in each document. Compounds, compounds described in Japanese Unexamined Patent Application Publication No. 2000-066385, Japanese Unexamined Patent Publication No. 2000-080068, Japanese Unexamined Patent Publication No. 2004-534797, Japanese Unexamined Patent Publication No. 2006-342166, International Publication No. WO2015/036910 The compound etc. described in are mentioned.

In commercial products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA Co., Ltd., a photopolymerization initiator described in Japanese Laid-Open Patent Publication No. 2012-14052) 2) is also suitably used. In addition, TR-PBG-304 (Changzhou Tronly New Electronic Materials Co., Ltd.), Adeka Arcles NCI-831 and Adeka Arcles NCI-930 (manufactured by ADEKA) Can also be used. In addition, DFI-091 (manufactured by Daito Chemicals Co., Ltd.) can also be used.

In addition, the compound described in Japanese Patent Publication No. 2009-519904 in which an oxime is connected to the N-position of the carbazole ring, the compound described in US Patent Publication No. 7626957 in which a hetero substituent is introduced at a benzophenone moiety, and a nitro group in the dye moiety are introduced. The compounds described in Patent Publication No. 2010-015025 and US Patent Publication No. 2009-292039, the ketoxime compound described in International Publication No. WO2009-131189, the triazine skeleton and the oxime skeleton described in US Patent Publication 7556910 in a molecule The compound, the compound described in Japanese Patent Application Laid-Open No. 2009-221114, which has an absorption maximum at 405 nm and good sensitivity to a g-ray light source, may be used.

Further, the cyclic oxime compounds described in JP 2007-231000 A and JP 2007-322744 A can also be suitably used. Among the cyclic oxime compounds, the cyclic oxime compounds condensed with the carbazole dye described in JP 2010-032985 A and JP 2010-185072 A are particularly preferable from the viewpoint of high light absorption and high sensitivity.

Moreover, the compound described in Japanese Unexamined Patent Publication No. 2009-242469, which is a compound having an unsaturated bond at a specific site of the oxime compound, can also be suitably used.

It is also possible to use an oxime compound having a fluorine atom. Specific examples of such an oxime compound include compounds described in Japanese Laid-Open Patent Publication No. 2010-262028, compounds 24 and 36 to 40 described in paragraph 0345 of Japanese Laid-Open Patent Publication 2014-500852, and Japanese Laid-Open Patent Publication 2013- And the compound (C-3) described in paragraph 0101 of 164471. As a specific example, the following compounds are mentioned.

[Formula 37]

As the most preferable oxime compound, an oxime compound having a specific substituent shown in JP 2007-269779 A, or an oxime compound having a thioaryl group shown in JP 2009-191061 A may be mentioned.

The photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, and a metallocene from the viewpoint of exposure sensitivity. Compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole Compounds selected from the group consisting of compounds and 3-aryl substituted coumarin compounds are preferred.

More preferable photopolymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzo At least one compound selected from the group consisting of a phenone compound, an acetophenone compound, and a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is preferable, It is more preferable to use a metallocene compound or an oxime compound, and an oxime compound is even more preferable.

In addition, the photoinitiator is N,N'-tetraalkyl-4,4'-diaminobenzophenone such as benzophenone and N,N'-tetramethyl-4,4'-diaminobenzophenone (Mihiler's ketone). , 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino- Aromatic ketones such as propanone-1, quinones condensed with aromatic rings such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkylbenzoin, benzyldimethyl ketal Benzyl derivatives such as may be used.

Moreover, a compound represented by the following formula (I) can also be used.

[Formula 38]

In formula (I), R ⁵⁰ represents an alkyl group having 1 to 20 carbon atoms; An alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms; An alkoxy group having 1 to 12 carbon atoms; Phenyl group; Alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 12 carbon atoms, halogen atom, cyclopentyl group, cyclohexyl group, alkenyl group having 1 to 12 carbon atoms, alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms And a phenyl group substituted with at least one of an alkyl group having 1 to 4 carbon atoms; Or biphenylyl, R ⁵¹ is a group represented by formula (II), or is the same group as R ^50, and R ⁵² to R ⁵⁴ are each independently C1-C12 alkyl, C1-C12 alkoxy or halogen It's Rosen.

[Formula 39]

In the formula, R ⁵⁵ to R ⁵⁷ are the same as R ⁵² to R ^{54 in} the formula (I).

Moreover, as a photoinitiator, the compound of paragraphs 0048 to 0055 of WO2015/125469 can also be used.

When the photosensitive resin composition contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and more preferably 0.1 with respect to the total solid content of the photosensitive resin composition. It is -10 mass%.

One type of photoinitiator may be sufficient, and two or more types may be sufficient as it. When there are two or more types of photoinitiators, it is preferable that the total is in the said range.

<<<migration inhibitor>>>

It is preferable that the photosensitive resin composition further contains a migration inhibitor. By including the migration inhibitor, it becomes possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the photosensitive resin composition layer.

The migration inhibitor is not particularly limited, but heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine A compound having a ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a 2H-pyran ring and a 6H-pyran ring, a triazine ring), thiourea and mercapto group And a hindered phenol compound, a salicylic acid derivative compound, and a hydrazide derivative compound. In particular, triazole-based compounds such as triazole and benzotriazole, and tetrazole-based compounds such as tetrazole and benzotetrazole can be preferably used.

Further, an ion trapping agent that captures anions such as halogen ions can also be used.

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of JP 2013-015701 A, the compound described in paragraphs 0073 to 0076 of JP 2009-283711 A, the compound described in paragraph 0052 of JP 2011-059656 A, The compounds described in paragraphs 0114, 0116 and 0118 of JP 2012-194520 A can be used.

Specific examples of migration inhibitors include 1H-1,2,3-triazole, 1H-1,2,4-triazole, and 1H-tetrazole.

When the photosensitive resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and 0.1 to 1.0% by mass relative to the total solid content of the photosensitive resin composition. More preferable.

Only one type of migration inhibitor may be used, and two or more types may be used. When there are two or more types of migration inhibitors, it is preferable that the total is within the above range.

<<<polymerization inhibitor>>>

It is preferable that the photosensitive resin composition used by this invention contains a polymerization inhibitor.

As a polymerization inhibitor, for example, hydroquinone, paramethoxyphenol, di-tert-butyl-paracresol, pyrogallol, para-tert-butylcatechol, parabenzoquinone, diphenyl-parabenzoquinone, 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, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2 ,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitro So-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 suitably used. Moreover, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817 A, and the compounds described in paragraphs 0031 to 0046 of WO2015/125469 can also be used.

When the composition has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the photosensitive resin composition.

Only one type of polymerization inhibitor may be used, and two or more types of polymerization inhibitors may be used. When there are two or more kinds of polymerization inhibitors, it is preferable that the total is within the above range.

<<<Thermal base generator>>>

The photosensitive resin composition used by this invention may contain a hot base generator.

The type of the hot base generator is not particularly determined, but includes at least one selected from an acidic compound that generates a base when heated to 40°C or higher, and an ammonium salt having an anion and an ammonium cation having a pKa1 of 0-4. It is preferable to include a hot base generator. Here, pKa1 represents the logarithm (-Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the acid, and details will be described later.

By blending such a compound, a cyclization reaction such as a polyimide precursor and a polybenzoxazole precursor can be performed at a low temperature, and a composition having more excellent stability can be obtained. In addition, since the hot base generator does not generate a base unless heated, it is possible to suppress cyclization of the polyimide precursor and the polybenzoxazole precursor during storage even when coexisting with the polyimide precursor and the polybenzoxazole precursor. Can be used, and storage stability is excellent.

The hot base generator preferably contains 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 and an ammonium cation having a pKa1 of 0-4. Do.

Since the acidic compound (A1) and the ammonium salt (A2) generate a base when heated, a cyclization reaction such as a polyimide precursor and a polybenzoxazole precursor can be accelerated by the base generated from these compounds. Cyclization of a mid precursor and a polybenzoxazole precursor can be performed at a low temperature. In addition, even if these compounds coexist with a polyimide precursor and a polybenzoxazole precursor that are cyclized and cured by a base, cyclization of the polyimide precursor and polybenzoxazole precursor, etc. hardly proceeds without heating, so stability A photosensitive resin composition containing such an excellent polyimide precursor and a polybenzoxazole precursor can be prepared.

In the present specification, with an acidic compound, 1 g of a compound is collected in a container, 50 mL of a mixture of ion-exchanged water and tetrahydrofuran (mass ratio is water/tetrahydrofuran = 1/4) is added, and at room temperature for 1 hour A solution obtained by stirring refers to a compound having a value of less than 7 measured at 20°C using a pH (power of hydrogen) meter.

In the present invention, the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40°C or higher, and more preferably 120 to 200°C. The upper limit of the base generation temperature is preferably 190°C or less, more preferably 180°C or less, and still more preferably 165°C or less. The lower limit of the base generation temperature is preferably 130°C or higher, and 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, it is difficult to generate a base during storage, so a photosensitive resin composition including a polyimide precursor and a polybenzoxazole precursor having excellent stability is prepared. can do. When the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200°C or less, the cyclization temperature of the polyimide precursor and the polybenzoxazole precursor can be lowered. The base generation temperature is, for example, using differential scanning calorimetry, heating the compound from 5°C/min to 250°C in an internal pressure capsule, reading the peak temperature of the lowest exothermic peak, and determining the peak temperature as base generation. It can be measured as temperature.

In the present invention, the base generated by the hot base generator is preferably a secondary amine or a tertiary amine, and more preferably a tertiary amine. Since the tertiary amine has high basicity, the cyclization temperature of the polyimide precursor and the polybenzoxazole precursor can be lowered. In addition, the boiling point of the base generated by the hot base generator is preferably 80°C or higher, more preferably 100°C or higher, and most preferably 140°C or higher.

Moreover, as for the molecular weight of the generated base, 80-2000 are preferable. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. In addition, the value of molecular weight is a theoretical value calculated|required from a structural formula.

In the present invention, the acidic compound (A1) preferably contains at least one selected from an ammonium salt and a compound represented by formula (101) or (102) described later.

In the present invention, the ammonium salt (A2) is preferably an acidic compound. Further, 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 at 40° C. or higher (preferably 120 to 200° C.). It may be a compound from which an acidic compound that generates a base upon heating has been removed.

In the present invention, the ammonium salt means a salt of an anion and an ammonium cation represented by the following formula (101) or (102). The anion may be bonded to any of the ammonium cations through a covalent bond, or may have it outside the molecule of the ammonium cation, but it is preferable to have it outside the molecule of the ammonium cation. In addition, when an anion has outside the molecule|numerator of an ammonium cation, it means a case where an ammonium cation and an anion are not bonded through covalent bond. Hereinafter, the anion outside the molecule of the cationic portion is also referred to as a counter anion.

Equation (101) Equation (102)

[Formula 40]

In formulas (101) and (102), R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and 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 in formulas (101) and (102) may be bonded to each other to form a ring.

It is preferable that the ammonium cation is represented by any one of the following formulas (Y1-1) to (Y1-5).

[Formula 41]

In formulas (Y1-1) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, and R ¹ and R ⁷ are the same as those of formula (101) or (102).

In formulas (Y1-1) to (Y1-5), Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group, n represents an integer of 1 or more, and m represents an integer of 0 to 5.

In the present invention, the ammonium salt preferably has an anion and an ammonium cation having a pKa1 of 0-4. The upper limit of pKa1 of an anion is more preferably 3.5 or less, and still more preferably 3.2 or less. As for the lower limit, 0.5 or more are preferable and 1.0 or more are more preferable. When the pKa1 of the anion is within the above range, the polyimide precursor and the polybenzoxazole precursor can be cyclized at low temperature, and further, the stability of the photosensitive resin composition including the polyimide precursor and the polybenzoxazole precursor can be improved. have. When pKa1 is 4 or less, the stability of the hot base generator is good, generation of a base can be suppressed without heating, and the stability of the photosensitive resin composition including a polyimide precursor and a polybenzoxazole precursor is good. When pKa1 is 0 or more, it is difficult to neutralize the generated base, and the cyclization efficiency of the polyimide precursor and the polybenzoxazole precursor is good.

The type of anion is preferably one selected from a carboxylic acid anion, a phenol anion, a phosphate anion, and a sulfate anion, and a carboxylate anion is more preferable because the stability of the salt and thermal decomposition can be compatible. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid 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 an anion of a divalent carboxylic acid. According to this aspect, it is possible to set as a hot base generator capable of further improving the stability, curability, and developability of a photosensitive resin composition containing a polyimide precursor and a polybenzoxazole precursor. In particular, by using an anion of a divalent carboxylic acid, stability, curability, and developability of a photosensitive resin composition including a polyimide precursor and a polybenzoxazole precursor can be further improved.

In the present invention, the carboxylic acid anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less. As for pKa1, 3.5 or less are more preferable, and 3.2 or less are still more preferable. According to this aspect, stability of the photosensitive resin composition containing a polyimide precursor, a polybenzoxazole precursor, etc. can be improved more.

Here, pKa1 represents the logarithm of the reciprocal of the dissociation constant of the acid's first proton, and Determination of Organic Structures by Physical Methods (authors: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; compilation: Braude) , EA, Nachod, FC; Academic Press, New York, 1955) or Data for Biochemical Research (author: Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using software of ACD/pKa (manufactured by ACD/Labs) will be used.

It is preferable that the carboxylate anion is represented by the following formula (X1).

[Formula 42]

In formula (X1), EWG represents an electron withdrawing group.

In the present invention, the electron withdrawing group means that the Hammett substituent constant σm represents a positive value. Here, σm is described in detail in the Review of Yuho Tsuno, Journal of the Japanese Organic Synthetic Chemistry Association Vol. 23, No. 8 (1965) p.631-642. In addition, the electron withdrawing group in this invention is not limited to the substituent described in the said document.

Examples of substituents in which σm represents a positive value include, for example, a CF ₃ group (σm=0.43), a CF ₃ CO group (σm=0.63), a HC≡C group (σm=0.21), and a CH ₂ =CH group (σm= 0.06), Ac group (σm=0.38), MeOCO group (σm=0.37), MeCOCH=CH group (σm=0.21), PhCO group (σm=0.34), H ₂ NCOCH ₂ group (σm=0.06), etc. I can. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group.

EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).

[Formula 43]

In formulas (EWG-1) to (EWG-6), R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group or a carboxyl group, and Ar represents an aromatic group.

In the present invention, it is preferable that the carboxylic acid anion is represented by the following formula (XA).

Expression (XA)

[Formula 44]

In formula (XA), L ¹⁰ represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an aromatic group, -NR ^X -and a combination thereof, and R ^X is a hydrogen atom, an alkyl group , An alkenyl group or an aryl group.

Specific examples of the carboxylic acid anion include maleic acid anion, phthalic acid anion, N-phenylimino diacetic acid anion, and oxalic acid anion. These can be used preferably.

As a specific example of a hot base generator, the following compounds are mentioned.

[Formula 45]

[Chemical Formula 46]

[Chemical Formula 47]

When using a hot base generator, the content of the hot base generator in the photosensitive resin composition is preferably 0.1 to 50% by mass with respect to the total solid content of the photosensitive resin composition. The lower limit is more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. As for the upper limit, 30 mass% or less is more preferable, and 20 mass% or less is still more preferable.

One type or two or more types of hot base generators can be used. When two or more types are used, it is preferable that the total amount is within the above range.

<<<Metal adhesion improver>>>

It is preferable that the photosensitive resin composition used by this invention contains a metal adhesiveness improving agent for improving the adhesiveness with metal materials used for an electrode, wiring, etc. Examples of the metal adhesion improving agent include sulfide compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A and paragraphs 0032 to 0043 of JP 2013-072935 A. As the metal adhesion improving agent, the following compounds (N-[3-(triethoxysilyl)propyl]maleic acid monoamide, etc.) are also illustrated.

[Formula 48]

The metal adhesion improving agent is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 15 parts by mass per 100 parts by mass of the resin. By setting it as 0.1 mass part or more, the adhesiveness between the cured film and a metal layer after a hardening process becomes favorable, and by setting it as 30 mass parts or less, the heat resistance and mechanical properties of the cured film after a hardening process become favorable.

Only one type of metal adhesive improving agent may be sufficient, and two or more types may be sufficient as it. When using two or more types, it is preferable that the total is in the above range.

<<<solvent>>>

When making the photosensitive resin composition used by this invention into a layer shape by coating, it is preferable to mix|blend a solvent. As the solvent, as long as the photosensitive resin composition can be formed in a layer shape, a known solvent can be used without limitation. Examples of the solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.

As esters, for example, ethyl acetate, 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 oxyacetic acid (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, methoxyacetic acid) Ethyl, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., 3-alkyloxypropionate methyl, 3-alkyloxypropionate ethyl, etc. (e.g., 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, etc.)), 2-alkyloxypropionic acid alkyl esters (e.g. 2-alkyloxy methyl propionate, 2 -Ethyl alkyloxypropionate, propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxy Ethyl propionate)), 2-alkyloxy-2-methyl methylpropionate and 2-alkyloxy-2-methyl ethylpropionate (e.g. 2-methoxy-2-methyl methylpropionate, 2-ethoxy-2-methyl Ethyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

As ethers, for example, 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 monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. are mentioned suitably.

As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like are suitably mentioned.

As aromatic hydrocarbons, toluene, xylene, anisole, limonene, etc. are mentioned suitably, for example.

As sulfoxides, dimethyl sulfoxide is preferably mentioned.

The solvent is also preferably a form in which two or more types are mixed from the viewpoint of improving the shape of the coated surface. 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 A mixed solution composed of two or more types is preferable. The combination of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

When the photosensitive resin composition has a solvent, the content of the solvent is preferably an amount such that the total solid content concentration of the photosensitive resin composition is 5 to 80% by mass, more preferably 5 to 70% by mass, from the viewpoint of coatability. , 10 to 60 mass% is particularly preferred. The content of the solvent may be adjusted according to the desired thickness and application method. For example, if the coating method is spin coat or slit coat, the content of the solvent that becomes the solid content concentration in the above range is preferable. If it is a spray coat, it is preferable to set it as 0.1 mass%-50 mass %, and it is preferable to set it as 1.0 mass%-25 mass %. By adjusting the content of the solvent according to the application method, a photosensitive resin composition layer having a desired thickness can be uniformly formed.

Only one type of solvent may be sufficient, and two or more types may be used. When there are two or more solvents, it is preferable that the total is within the above range.

In addition, the content of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide and N,N-dimethylformamide is photosensitive from the viewpoint of film strength. It is preferably less than 5% by mass, more preferably less than 1% by mass, particularly preferably less than 0.5% by mass, and more particularly preferably less than 0.1% by mass with respect to the total mass of the resin composition.

<<<Other additives>>>

The photosensitive resin composition used in the present invention is, as required, each kind of additive, such as a photobase generator, a thermal polymerization initiator, a thermal acid generator, a silane coupling agent, Sensitizing dyes, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like can be blended. In the case of blending these additives, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

(Photobase generator)

The photosensitive resin composition used by this invention may contain a photobase generator. Photobase generators are those that generate bases by exposure and do not show activity under normal conditions of room temperature and pressure, but are specifically limited as long as they generate bases (basic substances) when irradiated with electromagnetic waves and heated as external stimuli. It does not become. Since the base generated by exposure acts as a catalyst for curing a polyimide precursor, a benzoxazole precursor, or the like by heating, it can be suitably used in a negative type.

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

One type of photobase generator may be sufficient, and two or more types may be sufficient as it. When there are two or more types of photobase generators, it is preferable that the total is within the above range.

In the present invention, a known photobase generator can be used. For example, M. Shirai, and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Masahiro Tsunooka, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev., 211, 353(2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci. Technol., 13, 153 (2000); M. Winkle, and K. Graziano, J. Photopolym. Sci. Technol., 3, 419 (1990); M. Tsunooka, H. Tachi, and S. Yoshitaka, J. Photopolym. Sci. Technol., 9, 13 (1996); K. Suyama, H. Araki, M. Shirai, J. Photopolym. Sci. As described in Technol., 19, 81 (2006), a base component is a salt that has a structure such as a transition metal compound complex or an ammonium salt, or is latent by the amidine moiety forming a salt with a carboxylic acid. And ionic compounds neutralized by forming a nonionic compound in which a base component is latent by a urethane bond or an oxime bond such as a carbamate derivative, an oxime ester derivative, or an acyl compound.

The photobase generator that can be used in the present invention is not particularly limited, and known ones can be used. For example, carbamate derivatives, amide derivatives, imide derivatives, α cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives And oxime derivatives.

As photobase generators, for example, photobase generators having a cinnamic acid amide structure as disclosed in Japanese Laid-Open Patent Publication No. 2009-080452 and International Publication No. WO2009/123122, Japanese Laid-Open Patent Publication No. 2006-189591 and Japan A photobase generator having a carbamate structure as disclosed in Unexamined Patent Publication No. 2008-247747, an oxime structure and a carbamoyl oxime structure as disclosed in Japanese Unexamined Patent Publications 2007-249013 and 2008-003581 Although the photobase generator etc. which have are mentioned, it is not limited to these, In addition, a well-known photobase generator can be used.

In addition, as photobase generators, compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP 2012-093746 A, compounds described in paragraphs 0022 to 0069 of JP 2013-194205, Japanese Patent Application Laid-Open The compounds described in paragraphs 0026 to 0704 of Publication 2013-204019 A and the compounds described in paragraph 0052 of International Publication WO2010/064631 are exemplified.

(Thermal polymerization initiator)

The photosensitive resin composition used in the present invention may contain a thermal polymerization initiator (preferably a thermal radical polymerization initiator). As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used.

The thermal radical polymerization initiator is a compound that generates a radical by the energy of heat to initiate or accelerate the polymerization reaction of the polymerizable compound. When the cyclization reaction of the polyimide precursor and the polybenzoxazole precursor is advanced by adding a thermal radical polymerization initiator, the polymerization reaction of the polymerizable compound can be advanced. In addition, when the polyimide precursor and the polybenzoxazole precursor contain an ethylenically unsaturated bond, the polymerization reaction of the polyimide precursor and the polybenzoxazole precursor proceeds with cyclization of the polyimide precursor and the polybenzoxazole precursor. Since it can also be made, it becomes possible to achieve a higher degree of deterioration.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A.

When the photosensitive resin composition has a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.1 to 30% by mass, and more preferably 0.1 to 20% by mass based on the total solid content of the photosensitive resin composition. Mass% is particularly preferred. Moreover, it is preferable to contain 0.1-50 mass parts of a thermal radical polymerization initiator with respect to 100 mass parts of a polymeric compound, and it is more preferable to contain 0.5-30 mass parts. According to this aspect, it is easy to form a cured film more excellent in heat resistance.

One type of thermal radical polymerization initiator may be sufficient, and two or more types may be used. When there are two or more types of thermal radical polymerization initiators, it is preferable that the total is in the above range.

(Heat acid generator)

The photosensitive resin composition used by this invention may contain a thermal acid generator. The thermal acid generator generates an acid by heating and promotes cyclization of the polyimide precursor and the polybenzoxazole precursor to further improve the mechanical properties of the cured film. Further, the thermal acid generator has an effect of accelerating the crosslinking reaction of at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound, and a benzoxazine compound.

Examples of the thermal acid generator include those described in paragraph 0055 of Japanese Unexamined Patent Application Publication No. 2013-072935.

Further, the compound described in paragraph 0059 of JP 2013-167742 A is also preferable as a thermal acid generator.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the polyimide precursor and the polybenzoxazole precursor. By containing 0.01 parts by mass or more, since the crosslinking reaction and the cyclization of the polyimide precursor and the polybenzoxazole precursor are promoted, the mechanical properties and chemical resistance of the cured film can be further improved. Moreover, from the viewpoint of the electric insulation of the cured film, 20 parts by mass or less are preferable, 15 parts by mass or less are more preferable, and 10 parts by mass or less are particularly preferable.

Only one type of thermal acid generator may be used, and two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above range.

(Silane coupling agent)

The photosensitive resin composition used in the present invention may contain a silane coupling agent in order to improve adhesion to the substrate.

As an example of a silane coupling agent, the compound described in paragraphs 0062-0073 of JP 2014-191002 A, the compound described in paragraphs 0063-0071 of WO2011/080992A1, paragraphs 0060-0061 of JP 2014-191252 The compounds described in, the compounds described in paragraphs 0045 to 0052 of JP 2014-041264 A, and the compounds described in paragraph 0055 of International Publication No. WO2014/097594 are mentioned. Moreover, it is also preferable to use two or more different types of silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A.

The silane coupling agent is preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass per 100 parts by mass of the resin. If it is 0.1 mass part or more, more sufficient adhesiveness with a board|substrate can be provided, and if it is 20 mass part or less, problems, such as an increase in viscosity at the time of room temperature storage, can be suppressed more.

Only one type of silane coupling agent may be used, and two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above range.

(Sensitizing pigment)

The photosensitive resin composition used by this invention may contain a sensitizing dye. The sensitizing dye absorbs specific actinic radiation and enters an electron excited state. The sensitizing dye in an electron excited state is brought into contact with an amine generator, a thermal radical polymerization initiator, a photopolymerization initiator, and the like, and functions such as electron transfer, energy transfer, and heat generation occur. Thereby, the amine generator, the thermal radical polymerization initiator, and the photopolymerization initiator cause a chemical change and decompose to generate a radical, an acid or a base.

Examples of preferred sensitizing dyes include those belonging to the following compounds and having an absorption wavelength in the region of 300 nm to 450 nm. For example, polynuclear aromatics (e.g., phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (e.g., fluorescein, eosin, erythrosine) , Rhodamine B, rose bengal), thioxanthones (e.g., 2,4-diethylthioxanthone), cyanines (e.g., thiacabocyanine, oxacabocyanine), merocyanine Classes (e.g., merocyanine, carbomerocyanine), thiazines (e.g., thionin, methylene blue, toluidine blue), acridines (e.g., acridine orange, chloroflavin) , Acriflavin), anthraquinones (for example, anthraquinone), squaryliums (for example, squarylium), coumarins (for example, 7-diethylamino-4-methylcoumarin), And styrylbenzenes, distyrylbenzenes, carbazoles, and the like.

When the photosensitive resin composition contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20 mass%, more preferably 0.1 to 15 mass%, and 0.5 to 10 mass% with respect to the total solid content of the photosensitive resin composition. Is more preferred. A sensitizing dye may be used individually by 1 type, and may use 2 or more types together.

(Chain transfer agent)

The photosensitive resin composition used by this invention may contain a chain transfer agent. Chain transfer agents are defined, for example, on pages 683-684 of the 3rd edition of the Polymer Dictionary (Edition of the Polymer Society, 2005). As the chain transfer agent, a group of compounds having SH, PH, SiH, and GeH in the molecule is used, for example. These can donate hydrogen to a low-activity radical to generate a radical, or can generate a radical by deprotonating after being oxidized. In particular, thiol compounds (e.g., 2-mercaptobenzimidazole, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, 3-mercaptotriazole, 5-mercaptotetrazole Etc.) can be preferably used.

When the photosensitive resin composition has a chain transfer agent, the preferred content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, particularly preferably, based on 100 parts by mass of the total solid content of the photosensitive resin composition. Hagi is 1-5 parts by mass.

One type of chain transfer agent may be sufficient, and two or more types may be sufficient as it. When there are two or more types of chain transfer agents, it is preferable that the total is within the above range.

(Surfactants)

Each type of surfactant may be added to the photosensitive resin composition used in the present invention from the viewpoint of further improving the coatability. As the surfactant, various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used.

When the photosensitive resin composition has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass with respect to the total solid content of the photosensitive resin composition.

Only one type of surfactant may be used, and two or more types may be used. When there are two or more types of surfactants, it is preferable that the total is within the above range.

(Higher fatty acid derivative)

In the photosensitive resin composition used in the present invention, in order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added, and the composition may be unevenly distributed on the surface of the composition in the drying process after application.

When the photosensitive resin composition has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the photosensitive resin composition.

One type of higher fatty acid derivative may be sufficient, and two or more types may be used. When there are two or more types of higher fatty acid derivatives, it is preferable that the total is within the above range.

<<Characteristics of the photosensitive resin composition>>

Next, the characteristics of the photosensitive resin composition used in the present invention will be described.

It is preferable that the photosensitive resin composition used in the present invention has a crosslinked structure formed by exposure to lower solubility in an organic solvent. By having a crosslinked structure, when the photosensitive resin composition layer is laminated, the adhesion between the layers can be increased. In addition, the solubility of the photosensitive resin composition layer in the organic solvent is lowered by exposure, which is advantageous when providing deep grooves or deep holes when the number of layers is increased.

The moisture content of the photosensitive resin composition used 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 shape of the coated surface.

The metal content of the photosensitive resin composition used in the present invention is preferably less than 5 parts per million (ppm), more preferably less than 1 ppm by mass, and particularly preferably less than 0.5 ppm by mass from the viewpoint of insulating properties. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When a plurality of metals are included, it is preferable that the total of these metals is within the above range.

In addition, as a method of reducing metal impurities unintentionally included in the photosensitive resin composition, a raw material having a low metal content is selected as a raw material constituting the photosensitive resin composition, or filter filtration is performed on the raw material constituting the photosensitive resin composition. And a method of distilling under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.

In the photosensitive resin composition used in the present invention, the content of the halogen atom is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and particularly preferably less than 200 ppm by mass from the viewpoint of wiring corrosiveness. Among them, what is present in the form of a halogen ion is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and particularly preferably less than 0.5 ppm by mass. As a halogen atom, a chlorine atom and a bromine atom are mentioned. It is preferable that the sum of a chlorine atom and a bromine atom, or a chloride ion and a bromide ion each fall within the above range.

<Drying process>

The method for producing a laminate of the present invention may include a step of drying a solvent after forming the photosensitive resin composition layer. The preferred drying temperature is 50 to 150°C, more preferably 70 to 130°C, and still more preferably 90 to 110°C. As a drying time, 30 seconds-20 minutes are preferable, 1 minute-10 minutes are more preferable, 3 minutes-7 minutes are still more preferable.

<Exposure process>

The manufacturing method of the layered product of the present invention includes an exposure step of exposing the photosensitive resin composition layer. The conditions of exposure are not particularly determined, and it is preferable that the solubility of the exposed portion of the photosensitive resin composition in the developer can be changed, and it is more preferable that the exposed portion of the photosensitive resin composition can be cured. For example, the exposure is more preferably with respect to the photosensitive resin composition layer, it is preferable to 100 to investigate 10000mJ / cm ² in terms of exposure energy at a wavelength of 365nm, and irradiating 200 ~ 8000mJ / cm ^2.

The exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, and 240 to 550 nm is preferable.

Exposure may be performed by pattern exposure, or exposure may be performed by uniform irradiation of the entire surface.

<Development treatment process>

The manufacturing method of the laminate of the present invention includes a developing treatment step of performing a development treatment on the exposed photosensitive resin composition layer.

It is preferable that the developing treatment process is a negative developing process process. By performing the negative development process, a portion that is not exposed (non-exposed portion) is removed. The developing method is not particularly limited, and it is preferable that a desired pattern can be formed, and, for example, a developing method such as puddle, spray, immersion, or ultrasonic waves may be employed.

In the present invention, it is preferable to perform the development treatment step also when exposure is performed by uniform irradiation of the entire surface.

Development is preferably performed using a developer. The developer can be used without any particular limitation as long as the unexposed portion (non-exposed portion) is removed. Development with an organic solvent is preferable, and as esters, for example, ethyl acetate, acetic acid-n-butyl, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyric acid Butyl, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl oxyacetate (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g. , Methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionic acid alkyl esters (e.g., 3-alkyloxypropionate methyl, 3-alkyl Ethyl oxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), 2-alkyloxypropionate alkyl esters (e.g. : 2-alkyloxypropionate methyl, 2-alkyloxypropionate ethyl, 2-alkyloxypropionic acid propyl, etc. (e.g., 2-methoxypropionate methyl, 2-methoxypropionate ethyl, 2-methoxypropionate propyl, 2- Methyl ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., 2-methoxy-2-methylpropionate methyl , 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., as ethers, For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol Lycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monobutyl Ether, Propylene Glycol Monomethyl Ether, Propylene Glycol Monomethyl Ether Acetate, Propylene Glycol Monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like.

As ketones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc. are mentioned, for example.

As aromatic hydrocarbons, toluene, xylene, anisole, limonene, etc. are mentioned, for example.

As sulfoxides, dimethyl sulfoxide is preferably 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 preferred, Cyclopentanone and γ-butyrolactone are more preferable.

The developing time is preferably 10 seconds to 5 minutes.

Although the temperature at the time of development is not specifically determined, it can be performed at 20-40 degreeC normally.

After treatment with a developer, you may further rinse. It is preferable to perform rinse with a solvent different from a developer. For example, it can rinse using a solvent contained in a photosensitive resin composition. The rinse time is preferably from 5 seconds to 1 minute.

<hardening process>

The manufacturing method of the layered product of the present invention includes a curing step of curing the photosensitive resin composition layer after development treatment.

It is preferable that the curing step includes a temperature raising step of raising the temperature of the photosensitive resin composition layer, and a cooling step of cooling the photosensitive resin composition layer after the temperature raising step.

The curing step (especially the temperature raising step and the holding 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 resin. The oxygen concentration is preferably 50 vol ppm or less, and preferably 20 vol ppm or less.

<<heating process>>

It is preferable that the temperature raising step is a step of raising the temperature of the photosensitive resin composition layer to a temperature equal to or higher than the glass transition temperature.

In the temperature raising step, it is preferable to advance the cyclization reaction of the resin (preferably a polyimide precursor and a polybenzoxazole precursor) contained in the photosensitive resin composition layer. For example, in polyimide or polybenzoxazole, when heated together with a crosslinking agent, a three-dimensional network structure can be formed. Moreover, hardening of an unreacted radically polymerizable compound can also be advanced.

It is preferable that the final temperature reached in the temperature raising step is the imidization temperature of the resin contained in the photosensitive resin composition layer.

It is preferable that the final temperature reached in the temperature raising step is the highest heating temperature. As the maximum heating temperature, 100 to 500°C is preferable, 150 to 450°C is more preferable, and 160 to 350°C is still more preferable. In the method for producing a laminate of the present invention, it is particularly preferable from the viewpoint of stress relaxation that the final temperature reached in the temperature raising step is 250°C or less.

The temperature raising step is preferably performed at a temperature increase rate of 1 to 12°C/min from a temperature of 20 to 150°C to the maximum heating temperature, more preferably 2 to 11°C/min, and still more preferably 3 to 10°C/min. By setting the temperature rising rate to 1° C./min or more, excessive volatilization of amines can be prevented while ensuring productivity, and by setting the temperature rising rate to 12° C./min or less, the residual stress of the cured film can be relaxed.

The temperature at the start of heating is preferably 20 to 150°C, more preferably 20 to 130°C, and still more preferably 25 to 120°C. The temperature at the start of heating refers to the heating temperature at the time of starting the step of heating to the maximum heating temperature. For example, in the case of drying after applying the photosensitive resin composition on the substrate, it is the temperature after drying, and for example, it is preferable to gradually increase the temperature from the boiling point of the solvent contained in the photosensitive resin composition -(30 to 200)°C. .

Heating may be performed in stages. For example, even if a pretreatment process such as heating up to 25°C to 180°C at 3°C/min, placing at 180°C for 60 minutes, raising the temperature at 2°C/min to 180°C to 200°C for 120 minutes is performed, do. The heating temperature as a pretreatment step is preferably 100 to 200°C, more preferably 110 to 190°C, and most preferably 120 to 185°C. In this pretreatment step, it is also preferable to perform treatment while irradiating UV as described in US Patent Publication No. 9159547. It is possible to improve the properties of the cured film through such a pretreatment process. It is preferable to perform the pretreatment step in a short period of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment step may be two or more steps, for example, the pretreatment step 1 may be performed in the range of 100 to 150°C, and then the pretreatment step 2 may be performed in the range of 150 to 200°C.

The temperature raising step is preferably 20 to 200 minutes, more preferably 20 to 100 minutes, and particularly preferably 20 to 60 minutes.

<<Maintenance process>>

It is preferable that the manufacturing method of a laminated body of this invention includes a holding|maintenance process of maintaining at the same holding|maintenance temperature as the final reached temperature of a temperature raising process after a temperature raising process and before a cooling process.

After reaching the final reached temperature of the heating step, heating is preferably performed for 30 to 360 minutes at the same holding temperature as the final reached temperature of the heating step, more preferably 30 to 300 minutes, heating for 30 to 240 minutes It is particularly preferable to perform heating, and it is more particularly preferable to perform heating for 60 to 240 minutes.

The time taken for the holding process is called holding time.

It is preferable that the holding temperature in a holding process is 150-450 degreeC, and 160-350 degreeC is more preferable. In the method for producing a laminate of the present invention, it is particularly preferable from the viewpoint of stress relaxation that the holding temperature in the holding step is 250°C or less.

<<cooling process>>

It is preferable that the cooling process is a process of cooling a photosensitive resin composition layer at a temperature-fall rate of 2 degrees C/min or less after a temperature raising process.

It is preferable that it is 2 degreeC/min or less, and, as for the temperature-fall rate in a cooling process, it is more preferable that it is 1 degreeC/min or less. It is preferable from the viewpoint of stress relaxation that the temperature-fall rate in the cooling step is 0.1°C/min or more.

It is preferable from the viewpoint of stress relaxation that the temperature decrease rate in the cooling process is slower than the temperature increase rate in the temperature increase process.

The cooling process is preferably 30 to 600 minutes, more preferably 60 to 600 minutes, and particularly preferably 120 to 600 minutes.

In the method for manufacturing a laminate of the present invention, it is preferable from the viewpoint of stress relaxation that the time for the cooling step is longer than the time for the temperature increase step.

It is preferable that the final temperature reached in the cooling step is 30°C or more lower than the glass transition temperature (Tg) of the photosensitive resin composition layer (cured film) after the curing step. When the final temperature reached in the cooling step is lowered to a temperature 30° C. or more lower than the Tg of the photosensitive resin composition layer, the polyimide is sufficiently cured and it is easy to suppress the occurrence of delamination.

The final temperature reached in the cooling step is more preferably 160 to 250°C lower than the glass transition temperature of the photosensitive resin composition layer after the curing step, and particularly preferably 180 to 230°C.

<<The process of making room temperature>>

After the photosensitive resin composition layer reaches the final temperature reached in the cooling step, it is preferable to include a step of cooling the photosensitive resin composition layer at an arbitrary temperature-fall rate to bring it to room temperature.

There is no restriction|limiting in particular as for the temperature-fall rate of the process of making room temperature, It is preferable that it is faster than the temperature-fall rate of a cooling process. The rate of temperature decrease in the step of making room temperature can be, for example, 5 to 10°C/min.

<Metal layer formation process>

The method for producing a laminate of the present invention includes a metal layer forming step of forming a metal layer by vapor phase film formation on the surface of the photosensitive resin composition layer after the curing step,

The temperature of the photosensitive resin composition layer after the curing step when forming the metal layer is less than the glass transition temperature of the photosensitive resin composition layer after the curing step.

In the method for producing a laminate of the present invention, the temperature of the photosensitive resin composition layer when forming the metal layer is preferably 30°C or more lower than the glass transition temperature of the photosensitive resin composition layer, and more preferably 30 to 200°C, It is particularly preferable that it is 100 to 200°C low.

When there are two or more metal layers formed by the metal layer forming process, at least the temperature of the photosensitive resin composition layer after the curing process when forming a metal layer (preferably a barrier metal film) in direct contact with the photosensitive resin composition layer after the curing process is above It is preferably within the range. When there are two or more metal layers formed by the metal layer forming step, the temperature of the photosensitive resin composition layer after the curing step when forming the second metal layer is not particularly limited. However, even if it is the second metal layer, when there is a portion directly provided on the photosensitive resin composition layer, the temperature of the photosensitive resin composition layer after the curing step when forming the second metal layer is also preferably within the above range.

In particular, when forming the second metal layer using gas phase film formation, it is preferable that the temperature of the photosensitive resin composition layer after the curing step when forming the second metal layer is also within the above range. In addition, when forming the second metal layer using a non-gas-forming film (plating, etc.), generally, the temperature of the photosensitive resin composition layer after the curing step when forming the second metal layer is the glass transition temperature of the photosensitive resin composition layer. Becomes less than

As the metal layer formed by the metal layer forming step, an existing metal can be used without any particular limitation. As the metal contained in the metal layer formed by the metal layer forming process, a compound (including an alloy) containing at least one of copper, aluminum, nickel, vanadium, titanium, tantalum, chromium, cobalt, gold and tungsten It is illustrated. In the method for producing a laminate of the present invention, it is more preferable that the metal layer formed by the metal layer forming step contains at least one type of titanium, tantalum, and copper, and a compound containing at least one of them, and titanium and copper And it is particularly preferable to contain at least one of the compounds containing at least one of these, and more particularly preferably containing copper. As a specific example of the case where the metal layer contains at least one type of titanium, tantalum, copper and a compound containing at least one of these, a metal layer made of titanium, tantalum, copper, TiN, TaN, or TiW can be mentioned. And a metal layer made of titanium, tantalum, copper, TiN, or TiW is preferable. The number of metals contained in the metal layer formed by the metal layer forming step may be one or two or more.

In the method for producing a laminate of the present invention, the thickness of the metal layer formed by the metal layer forming step is preferably 50 to 2000 nm, more preferably 50 to 1000 nm, and particularly preferably 100 to 300 nm.

In the method for producing a laminate of the present invention, the metal layer formed by the metal layer forming step may be one layer or two or more layers.

When the metal layer formed by the metal layer forming step is one layer, the metal layer is preferably used as a barrier metal film.

When there are two or more metal layers formed by the metal layer forming process, it is preferable that the thickness of the entire metal layer formed by the metal layer forming process is within the above range. When there are two or more metal layers formed by the metal layer forming step, it is preferable that the metal layer formed by the metal layer forming step is a laminate of a barrier metal film and a seed layer.

It is preferable that the barrier metal film is a layer capable of shortening the penetration length of the metal into the cured film. It is preferable that the type of the metal of the barrier metal film is the metal included in the metal layer formed by the metal layer forming step and is the metal described above. The thickness of the barrier metal film is preferably 50 to 2000 nm, more preferably 50 to 1000 nm, and particularly preferably 100 to 300 nm.

The seed layer is preferably a layer for making it easy to form a pattern of the second metal layer formed by the second metal layer forming step. It is preferable that the type of the metal of the seed layer is the same type of metal as the second metal layer formed by the second metal layer forming step. The thickness of the seed layer is preferably 50 to 2000 nm, more preferably 50 to 1000 nm, and particularly preferably 100 to 300 nm.

The method of forming the metal layer is not particularly limited, and an existing vapor phase film forming method can be applied. For example, a sputtering method, a chemical vapor deposition (CVD) method, a plasma method, and a combination thereof may be considered. Among these, the method of forming the metal layer is preferably a sputtering method from the viewpoint of film thickness control.

<Second metal layer formation process>

It is preferable that the manufacturing method of the laminated body of the present invention further includes a second metal layer forming step of forming a second metal layer on the surface of the metal layer.

As the second metal layer formed by the second metal layer forming step, an existing metal may be used without particular limitation. Examples of metals included in the second metal layer formed by the second metal layer forming process include copper, aluminum, nickel, vanadium, titanium, tantalum, chromium, cobalt, gold, and tungsten. In the method for producing a laminate of the present invention, it is preferable that the second metal layer contains copper from the viewpoint of using the laminate of the present invention as a redistribution layer of a semiconductor element.

In the manufacturing method of the laminate, the thickness of the second metal layer formed by the second metal layer forming step is, for example, 3 to 50 μm, preferably 3 to 10 μm, more preferably 5 to 10 μm, and 5 to 7 μm It is particularly preferred. When manufacturing a laminate for use in power semiconductors, it is preferable that the thickness of the second metal layer formed by the second metal layer forming step is 35 to 50 μm.

The method of forming the second metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, and JP 2004-101850 A can be used. For example, photolithography, lift-off, chemical vapor deposition (CVD), electrolytic plating, electroless plating, etching, printing, and a combination thereof can be considered. More specifically, a patterning method combining photolithography and etching, a patterning method combining photolithography and electroplating, and a patterning method combining photolithography, electrolytic plating and etching may be mentioned.

As a patterning method that combines photolithography and electroplating, after sputtering a seed layer of the metal layer formed by the metal layer forming process, a pattern of the seed layer is formed by photolithography, and electrolytic plating is applied on the seed layer on which the pattern is formed. A method of performing to form the second metal layer is preferred. After that, etching may be further performed to remove the seed layer in the region where the second metal layer is not formed.

<Surface activation treatment process>

The manufacturing method of the laminate may include a surface activation treatment step of surface activation treatment of at least a part of the metal layer and the photosensitive resin composition layer.

It is preferable to perform the surface activation treatment process usually after a metal layer formation process. After the curing step, after performing a surface activation treatment step on the photosensitive resin composition layer, a metal layer may be formed.

Surface activation treatment may be performed only on at least part of the metal layer, may be performed only on at least part of the photosensitive resin composition layer after the curing step, and performed on at least a part of both the metal layer and the photosensitive resin composition layer after the curing step. Also works. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is more preferable to further perform the surface activation treatment on a part or all of the region in which the photosensitive resin composition layer is formed on the metal layer. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion to the cured film provided on the surface can be improved.

Moreover, it is preferable to perform surface activation treatment also about part or all of the photosensitive resin composition layer (cured film) after a hardening process. In this way, by performing the surface activation treatment on the surface of the photosensitive resin composition layer, the adhesion with the metal layer or cured film provided on the surface-activated surface can be improved. In the case of negative development, since the exposed portion is subjected to surface treatment and the strength of the film is improved by curing or the like, the photosensitive resin composition layer (cured film) is not damaged.

Specific examples of the surface activation treatment include plasma treatment of each type of source gas (oxygen, hydrogen, argon, nitrogen, nitrogen and hydrogen mixed gas, argon and oxygen mixed gas, etc.); Corona discharge treatment; Etching treatment using a mixed gas of CF ₄ and O _{2, a} mixed gas of NF ₃ and O ₂ , SF ₆ and NF _3, and a mixed gas of NF ₃ and O ₂ ; Surface treatment using an ultraviolet (UV) ozone method; Immersion treatment in an organic surface treatment agent containing a compound having at least one amino group and thiol group after immersion in an aqueous hydrochloric acid solution to remove the oxide film; It is preferably selected from mechanical roughening treatment using a brush. Plasma treatment is more preferred, and oxygen plasma treatment using oxygen as the source gas is particularly preferred. For the corona discharge treatment, energy, 500 ~ 200000J / m ² are preferred, and more preferably 1000 to the ^{100000J / m 2, 10000 ~ 50000J} / m 2 is more preferred.

<Lamination process>

In the manufacturing method of the laminate of the present invention, it is preferable to further perform the photosensitive resin composition layer forming step, the exposure step, the developing treatment step, the curing step, and the metal layer forming step in the above order after the metal layer forming step. . In this case, since the metal layer forming process is repeated, the effect of suppressing delamination in particular when the substrate, the cured film, and the metal layer are laminated is great.

In this specification, after the metal layer forming step, a step of further performing a photosensitive resin composition layer forming step, an exposure step, a developing treatment step, a curing step, and a metal layer forming step in the above order is referred to as a lamination step. The lamination step is more preferably a step of performing the photosensitive resin composition layer forming step, the exposure step, the developing treatment step, the curing step, the metal layer forming step, and the second metal layer forming step in the above order.

When the lamination process is further performed after the lamination process, the surface activation treatment process can be further performed after the exposure process or after the metal layer formation process.

It is preferable to perform the said lamination process 3-7 times, and it is more preferable to perform 3-5 times.

For example, a cured film such as a cured film/metal layer/cured film/metal layer/cured film/metal layer is preferably in a configuration of 3 or more and 7 or less layers, and more preferably 3 or more and 5 or less layers. The more the multilayered configuration is, the more the photosensitive resin composition layer is repeatedly exposed to a developer, a metal etching treatment, or a high-temperature treatment in the curing step, the metal layer/cured film interface resulting from the method of manufacturing the laminate of the present invention, or curing. The effect of suppressing the occurrence of delamination at the film/cured film interface is exhibited.

By setting it as such a structure, a photosensitive resin composition layer (cured film) and a metal layer can be laminated|stacked alternately, and can be used as a multilayer wiring structure of a semiconductor element, such as a redistribution layer.

It is preferable that the thickness of the photosensitive resin composition layer (cured film) becomes thicker as the lamination goes upward.

[Laminate]

The laminate of the present invention has a substrate, a pattern cured film, and a metal layer positioned on the surface of the pattern cured film,

The patterned cured film contains polyimide or polybenzoxazole,

The penetration of the metal constituting the metal layer located on the surface of the pattern cured film into the pattern cured film is 130 nm or less from the surface of the pattern cured film.

<Pattern cured film>

It is preferable that the patterned cured film in the laminate of the present invention is a photosensitive resin composition layer after the curing step in the method for producing a laminate of the present invention.

<<Tg>>

It is preferable that the glass transition temperature of the pattern cured film (photosensitive resin composition layer after a curing process) is 150-300 degreeC, it is more preferable that it is 160-250 degreeC, and it is especially preferable that it is 180-230 degreeC.

<<residual stress>>

The patterned cured film (photosensitive resin composition layer after the curing step. Preferably, the photosensitive resin composition layer after the metal layer forming step. More preferably, the photosensitive resin composition layer after the metal layer forming step and the second metal layer forming step) was measured according to the laser measurement method. It is preferable that the residual stress is less than 35 MPa, more preferably less than 25 MPa, and particularly preferably less than 15 MPa.

<Metal layer>

It is preferable that the metal layer in the laminate of the present invention is a metal layer formed by a metal layer forming step in the method for producing a laminate of the present invention.

Further, the metal layer in the laminate of the present invention may be a laminate of a metal layer formed by the metal layer forming step in the method for producing a laminate of the present invention and a second metal layer formed by the second metal layer forming step. In this case, the metal layer formed by the metal layer forming step in the method for producing a laminate of the present invention and the second metal layer formed by the second metal layer forming step may be integrated to form a metal layer in the laminate of the present invention. .

In addition, the metal layer formed by the metal layer forming step in the method for producing a laminate of the present invention is, for example, two layers of a barrier metal film and a seed layer, and the second metal layer formed by the second metal layer forming step is a seed layer. In the case of the same type of metal as, only the seed layer and the second metal layer may be integrated. In this case, the layer in which only the seed layer and the second metal layer are integrated and the layered product of the barrier metal film may be a metal layer in the layered product of the present invention.

The thickness of the metal layer in the laminate of the present invention is preferably 0.1 to 50 μm, and more preferably 1 to 10 μm in the thickest part.

It is preferable that the metal layer in the laminate of the present invention is a flat metal layer from the viewpoint of stabilizing the film quality of the metal layer. By forming the metal layer using a sputtering method, a flat metal layer can be formed. In addition, by forming a metal layer by sputtering under the condition that the temperature of the photosensitive resin composition layer after the curing process when forming the metal layer is less than the glass transition temperature of the photosensitive resin composition layer after the curing process, a flatter metal layer can be formed. I can.

<The penetration length of the metal into the patterned cured film>

The penetration length of the metal constituting the metal layer positioned on the surface of the patterned cured film into the patterned cured film is 130 nm or less, preferably 50 nm or less, and more preferably 30 nm or less from the surface of the pattern cured film.

[Method of manufacturing semiconductor device]

The method for manufacturing a semiconductor device of the present invention includes a method for manufacturing a laminate of the present invention.

With the above configuration, the method of manufacturing a semiconductor device of the present invention can provide a semiconductor device in which delamination is suppressed when a substrate, a cured film, and a metal layer are stacked.

Hereinafter, an embodiment of a semiconductor device obtained by the method for manufacturing a semiconductor device of the present invention will be described.

1 is a schematic diagram showing a configuration of an embodiment of a semiconductor element. The semiconductor element 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a semiconductor chip 101 in which a plurality of semiconductor chips 101a to 101d are stacked is disposed on a wiring board 120.

In addition, in this embodiment, the case where the number of stacked semiconductor chips is 4 is mainly described, but the number of stacked semiconductor chips is not particularly limited, and for example, 2 layers, 8 layers, 16 layers, 32 layers, etc. may be used. . Moreover, it may be the first floor.

Each of the plurality of semiconductor chips 101a to 101d is made of a semiconductor wafer such as a silicon substrate.

The uppermost semiconductor chip 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof.

The semiconductor chips 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) integrally provided with the through electrodes are provided on both surfaces of each semiconductor chip.

The semiconductor chip 101 has a structure in which a semiconductor chip 101a having no through electrodes and semiconductor chips 101b to 101d having through electrodes 102b to 102d are flip-chip connected.

That is, the electrode pad of the semiconductor chip 101a not having a through electrode and the connection pad on the side of the semiconductor chip 101a of the semiconductor chip 101b having the through electrode 102b adjacent thereto are metals such as solder bumps. It is connected by bump 103a. The connection pad on the other side of the semiconductor chip 101b having the through electrode 102b is a connection pad on the semiconductor chip 101b side of the semiconductor chip 101c having the through electrode 102c adjacent thereto, It is connected by metal bumps 103b such as solder bumps. Similarly, the connection pad on the other side of the semiconductor chip 101c having the through electrode 102c is the connection pad on the semiconductor chip 101c side of the semiconductor chip 101d having the through electrode 102d adjacent thereto. And a metal bump 103c such as a solder bump.

An underfill layer 110 is formed in the gap between each of the semiconductor chips 101a to 101d, and each of the semiconductor chips 101a to 101d is stacked through the underfill layer 110.

The semiconductor chip 101 is stacked on the wiring board 120.

As the wiring board 120, a multilayer wiring board using an insulating substrate such as a resin substrate, a ceramics substrate, and a glass substrate as a base material is used. As the wiring board 120 to which a resin substrate is applied, a multilayer copper clad laminate (multilayer printed wiring board), etc. are mentioned.

A surface electrode 120a is provided on one surface of the wiring board 120.

Between the wiring board 120 and the semiconductor chip 101, an insulating layer 115 on which a redistribution layer 105 is formed is disposed, and the wiring board 120 and the semiconductor chip 101 are provided with a redistribution layer 105 It is electrically connected through. As the insulating layer 115, a photosensitive resin composition layer (cured film) after the curing step in the present invention can be used. As the insulating layer 115 on which the redistribution layer 105 is formed, a laminate obtained by the method for producing a laminate of the present invention can be used.

One end of the redistribution layer 105 is connected to an electrode pad formed on the surface of the semiconductor chip 101d on the side of the redistribution layer 105 through metal bumps 103d such as solder bumps. In addition, the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board through a metal bump 103e such as a solder bump.

In addition, an underfill layer 110a is formed between the insulating layer 115 and the semiconductor chip 101. In addition, an underfill layer 110b is formed between the insulating layer 115 and the wiring board 120.

2 is a schematic diagram showing the configuration of an embodiment of a laminate obtained by the method for producing a laminate of the present invention. Fig. 2 shows an example in which the laminate obtained by the method for producing a laminate of the present invention is used as a redistribution layer. In Fig. 2, 200 denotes a laminate obtained by the method of the present invention, 201 denotes a photosensitive resin composition layer (cured film), and 203 denotes a metal layer. In Fig. 2, the metal layer 203 is a layer indicated by an oblique line. The photosensitive resin composition layer 201 is formed in a desired pattern by negative development. The metal layer 203 is formed so as to cover a part of the surface of the pattern, and a photosensitive resin composition layer (cured film) 201 is further laminated on the surface of the metal layer 203. Then, the photosensitive resin composition layer (cured film) acts as an insulating layer, the metal layer acts as a redistribution layer, and is introduced as a redistribution layer in the above-described semiconductor element.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. Materials, usage, ratios, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" are based on mass unless otherwise specified.

[Example 1]

<Synthesis of polyimide precursor>

Synthesis of polyimide precursor Aa-1 (polyimide precursor having a radical polymerizable group) from <<4,4'-oxydiphthalic dianhydride, 4,4'-oxydianiline and 2-hydroxyethyl methacrylate >>

20.0 g (64.5 mmol) of 4,4'-oxydiphthalic acid dianhydride (4,4'-oxydiphthalic acid dried at 140° C. for 12 hours) and 18.6 g (129 mmol) of 2-hydroxyethyl meta It mixed with acrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diglyme (diethylene glycol dimethyl ether). The mixture was stirred at a temperature of 60° C. for 18 hours to prepare a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Then, the reaction mixture was cooled to -10°C and 16.12 g (135.5 mmol) of SOCl ₂ were added over 10 minutes while maintaining the temperature at -10±4°C. After the reaction mixture was diluted with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution in which 11.08 g (58.7 mmol) of 4,4'-oxydianiline was dissolved in 100 ml of N-methylpyrrolidone was added dropwise to the reaction mixture at 20 to 23°C for 20 minutes. Then, the reaction mixture was stirred at room temperature overnight. Then, the reaction mixture was added to 5 liters of water, and the polyimide precursor was precipitated. The mixture of water and the polyimide precursor was stirred for 15 minutes at a speed of 5000 rpm. The mixture of water and the polyimide precursor was filtered, the filtrate was removed, and the residue containing the polyimide precursor was added to 4 liters of water. The mixture of water and the polyimide precursor was stirred for another 30 minutes, filtered again, and a polyimide precursor was obtained as a residue. Next, the obtained polyimide precursor was dried at 45° C. for 3 days under reduced pressure to obtain a polyimide precursor Aa-1.

The structure of the polyimide precursor Aa-1 is shown below.

[Chemical Formula 49]

<Preparation of photosensitive resin composition>

The following components were mixed, and the photosensitive resin composition was prepared as a uniform solution.

<<Composition of photosensitive resin composition A-1>>

Resin: 32 parts by mass of polyimide precursor (Aa-1)

Polymerizable compound B-1 6.9 parts by mass

1.0 parts by mass of photopolymerization initiator C-1

Polymerization inhibitor: 0.08 parts by mass of parabenzoquinone (manufactured by Tokyo Kasei Kogyo)

Migration inhibitor: 1H-tetrazole (manufactured by Tokyo Kasei Kogyo)

0.12 parts by mass

Metal adhesion improving agent: 0.70 parts by mass of N-[3-(triethoxysilyl)propyl]maleic acid monoamide

Solvent: 48.00 parts by mass of γ-butyrolactone

Solvent: 12.00 parts by mass of dimethyl sulfoxide

<<Composition of photosensitive resin composition A-2>>

Resin: 32 parts by mass of polyimide precursor (Aa-1)

Polymerizable compound B-1 6.9 parts by mass

1.0 parts by mass of photopolymerization initiator C-1

Polymerization inhibitor: 2,6-di-tert-butyl-4-methylphenol (manufactured by Tokyo Kasei Kogyo)

0.1 parts by mass

Migration inhibitor: 1H-1,2,4-triazole (made by Tokyo Kasei Kogyo) 0.1 parts by mass

Solvent: 48.00 parts by mass of γ-butyrolactone

Solvent: 12.00 parts by mass of dimethyl sulfoxide

The details of each additive are as follows.

B-1: NK ester A-9300 (Shin-Nakamura Chemical Industry Co., Ltd. product, trifunctional acrylate, the following structure)

[Formula 50]

(C) photopolymerization initiator

C-1: Compound 24 described in paragraph 0345 of Japanese Laid-Open Patent Publication No. 2014-500852

[Formula 51]

<Filtration process>

Each photosensitive resin composition was filtered under pressure by passing through a filter having a width of 0.8 μm.

<Photosensitive resin composition layer formation process>

Thereafter, each photosensitive resin composition was applied on a silicon wafer by a spin coating method to form a layer shape, and a photosensitive resin composition layer was formed.

<Drying process>

The silicon wafer having the obtained photosensitive resin composition layer was dried on a hot plate at 100° C. for 5 minutes to obtain a photosensitive resin composition layer having a uniform thickness of 20 μm on the silicon wafer.

<Exposure process>

Next, the photosensitive resin composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ/cm ² at an exposure wavelength of 365 nm (i-line) using a stepper (Nikon NSR 2005 i9C) (uniform irradiation on the entire surface).

In this embodiment, in order to facilitate the measurement of the stress, the entire surface is exposed by uniform irradiation, immersed in a developer, and a cured film is formed through a curing step. However, you may pattern exposure, immerse in a developer, remove an unexposed part, and may form a cured film with a pattern formed through a hardening process.

When the photosensitive resin composition layer is patterned, more interfaces are generated than when not patterned, and a location with a small contact area occurs between the layers when the substrate, the cured film, and the metal layer are laminated. In this case, delamination is more likely to occur, and the effect of the present invention is more remarkably obtained.

<Development treatment process>

The photosensitive resin composition layer exposed on the entire surface was immersed in cyclopentanone for 60 seconds to perform development treatment.

<hardening process>

Subsequently, the photosensitive resin composition layer after the developing treatment was cured by the following methods (1) to (4).

<<(1) Heating process>>

First, in a nitrogen atmosphere with an oxygen concentration of 20 volume ppm or less, a substrate having a photosensitive resin composition layer after development is placed on a temperature-adjustable plate, and the temperature is increased from room temperature (20°C) to a temperature increase rate of 10°C/min, Heated to the final temperature reached 230° C. for 21 minutes.

<<(2) Maintenance process>>

Thereafter, the photosensitive resin composition layer was held at 230°C for 3 hours, which is the final temperature reached (holding temperature) in the temperature raising step.

<<(3) Cooling process>>

The photosensitive resin composition layer after heating for 3 hours in the holding step was slowly cooled from 230° C. to the final temperature reached 170° C. of the cooling step for 30 minutes at a rate of 2° C./min.

<<(4) Process to make room temperature>>

After the photosensitive resin composition layer reached the final temperature of 170°C in the cooling step, the photosensitive resin composition layer was cooled at a temperature reduction rate of 5 to 10°C/min to room temperature to obtain a cured film.

<Metal layer formation process>

Next, in a sputtering device (manufactured by AMAT, product name Endura), on the photosensitive resin composition layer after the curing step, by sputtering, under the condition that the temperature of the photosensitive resin composition layer is 150°C, 100 nm of Ti was formed as a barrier metal film. The first metal layer to be used was formed, and 300 nm of Cu was continuously formed to form a second metal layer to be used as a seed layer.

The thickness of the entire metal layer formed in the metal layer forming step using the sputtering method was 400 nm.

In the sputtering device, the temperature of the photosensitive resin composition layer is measured by observing the change in color by attaching a seal (thermolabel, Nichiyu Kiken Kogyo Co., Ltd.) that changes the temperature of the surface of the photosensitive resin composition layer to temperature. I got it.

<Second metal layer formation process>

Then, a dry film resist (manufactured by Hitachi Kasei Co., Ltd., trade name Photec RY-3525) was adhered on the seed layer with a roll laminator, and the patterned photo tool was adhered to each other, and EXM- manufactured by Oak Seisakusho Co., Ltd. Using a 1201 type exposure machine, exposure was performed with an energy amount of 100 mJ/cm ² . Next, spray development was performed for 90 seconds with a 1 mass% sodium carbonate aqueous solution at 30°C to open the dry film resist. Next, a copper plating layer having a thickness of 7 μm was formed on the dry film resist and on the seed layer in the portion where the dry film resist was opened by using an electrolytic copper plating method. Next, the dry film resist was peeled using a peeling liquid. Next, the seed layer (300 nm Cu layer) of the portion from which the dry film resist was peeled was removed using an etching solution, and a patterned metal layer was formed on the surface of the photosensitive resin composition layer after the curing step.

<Characteristics of the cured film>

<<Measurement of glass transition temperature>>

With respect to the photosensitive resin composition layer (cured film) after the curing step, the glass transition temperature was measured by the following method.

It was set in the dynamic viscoelasticity measuring apparatus, and it heated up from 0 degreeC to 350 degreeC by the tensile method, the frequency of 1Hz and the temperature rising rate of 10 degreeC/min, and Tg was calculated|required from the peak temperature of tan delta.

The obtained results are shown in Table 1 below.

<<Measurement of stress>>

With respect to the photosensitive resin composition layer (cured film) after the metal layer forming step and the second metal layer forming step, the stress was measured by the following method.

About the silicon wafer before application|coating of the photosensitive resin composition layer, the wafer was set in a thin film stress measuring apparatus, and it laser-scanned under room temperature, and the blank value was calculated|required.

A wafer on which a photosensitive resin composition layer (cured film) was formed after a metal layer forming step and a second metal layer forming step was formed in a thin film stress measuring device, and after laser scanning at room temperature, compared with the blank value before application of the photosensitive resin composition layer, The stress was measured from the film thickness and the radius of curvature.

The obtained results are shown in Table 1 below.

<Lamination process>

In addition, on the surface where the irregularities are formed by the metal layer and the photosensitive resin composition layer after the curing step, again, using the same photosensitive resin composition, the procedure from the filtration step of the photosensitive resin composition to the curing step is performed again in the same manner as above. , A laminate having two layers of the photosensitive resin composition layer after the curing step was formed.

Further, with respect to the laminate having two layers of the photosensitive resin composition layer after the curing step, the metal layer forming step and the second metal layer forming step were again performed in the same manner as above to form a laminate.

<Evaluation of laminate>

<<Measurement of penetration length of metal into cured film>>

With respect to the laminate after the metal layer forming step and the second metal layer forming step, the measurement of the penetration length of the metal into the cured film after the metal layer forming step using the sputtering method was performed by the following method.

Measurement is performed by direct observation of the cross section by a focused ion beam (FIB) and a transmission electron microscope (TEM), and a high-angle annular dark-field scanning transmission electron microscopy; HAADF-STEM) and electron energy loss spectroscopy (EELS) were used in combination to perform elemental analysis.

The obtained results are shown in Table 1 below.

<< Peel test after cycle test >>

With respect to the laminate after the lamination process, the peel test after the cycle test was performed by the following method.

Each layered product was cooled in nitrogen at -55°C for 30 minutes, and thereafter, 500 cycles of heating at 125°C for 30 minutes were performed. After that, cut out each of the laminates so that the width is 5 mm in the vertical direction with respect to the surface of the cured film, the portion where the cured film and the metal layer are in contact, and the portion where the metal layer and the second metal layer are in contact, respectively, It observed, and the presence or absence of peeling between a cured film and a metal layer, and between a metal layer and a 2nd metal layer in one cut-out was confirmed with an optical microscope. It is preferably "no peeling".

The obtained results are shown in Table 1 below.

[Examples 2 to 6 and Comparative Examples 1 to 3]

Except having changed to the conditions shown in the following table, it carried out similarly to Example 1, and produced the laminated body of Examples 2-6 and Comparative Examples 1-3.

In the same manner as in Example 1, the properties of the cured film were measured and the laminate was evaluated.

[Table 1]

From Table 1 above, when the temperature of the photosensitive resin composition layer after the curing process when forming the metal layer is less than the glass transition temperature of the photosensitive resin composition layer after the curing process, the residual stress of the cured film is small, and the metal layer forming process using the sputtering method It was found that a laminate having a short penetration length of the metal afterwards can be provided. In the laminate of the present invention where the residual stress of the cured film is small and the penetration length of the metal is short, it has been found that delamination can be suppressed when the substrate, the cured film, and the metal layer are laminated.

On the other hand, from Comparative Examples 1 to 3, when the temperature of the photosensitive resin composition layer after the curing step when forming the metal layer is equal to or higher than the glass transition temperature of the photosensitive resin composition layer after the curing step, the residual stress of the cured film is large, and the sputtering method is used. A laminate having a long penetration length of the metal after the metal layer forming step to be used was obtained. In the laminates of Comparative Examples 1 to 3 in which the residual stress of the cured film was large and the penetration length of the metal was long, it was found that delamination occurs when the substrate, the cured film, and the metal layer are laminated.

In Example 1, the metal layer (copper thin film) was changed to an aluminum thin film, and other things were carried out in the same manner. As in Example 1, good results were obtained.

In Example 1, except that the solid content concentration of the photosensitive resin composition 1 was 1/10 without changing the composition ratio, and spray-coated using a spray gun ("NanoSpray" manufactured by Austria EV Group (EVG)), Examples In the same manner as in 1, a laminate was formed. As in Example 1, excellent effects were obtained.

In the production of the laminate of Example 1, a laminate was prepared in the same manner as in Example 1 except that heating (pretreatment) was performed at 100° C. for 10 minutes before heating at 230° C. for 3 hours. Evaluated. As in Example 1, excellent effects were obtained.

In the manufacture of the laminate of Example 1, a laminate was produced in the same manner as in Example 1, except that heating (pretreatment) was performed at 150° C. for 10 minutes before heating at 230° C. for 3 hours. Evaluated. As in Example 1, excellent effects were obtained.

In the manufacture of the laminate of Example 1, the laminate was carried out in the same manner as in Example 1 except that heating (pretreatment) was performed at 180° C. for 10 minutes while irradiating with UV light before heating at 230° C. for 3 hours. Was prepared and properties were evaluated. As in Example 1, excellent effects were obtained.

Industrial availability

The laminate produced by the method for producing a laminate of the present invention can suppress delamination when a substrate, a cured film, and a metal layer are laminated. In addition, in the laminate produced by the method for producing a laminate of the present invention, even when two or more sets of laminates of a substrate, a cured film, and a metal layer are laminated, delamination can be suppressed. Such a laminate can be used to manufacture an interlayer insulating layer for a redistribution layer of a semiconductor device, and can provide an interlayer insulating layer for a redistribution layer in which delamination is suppressed. In addition, such a laminate can be used to manufacture an interlayer insulating layer for power semiconductor applications, a film or a single layer insulating layer among copper fillers for a three-dimensional integrated circuit (IC), and an interlayer insulating layer for a panel use.

100: semiconductor device
101, 101a~101d: semiconductor chip
102b, 102c, 102d: through electrode
103a~103e: metal bump
105: redistribution layer
110, 110a, 110b: underfill layer
115: insulating layer
120: wiring board
120a: surface electrode
200: laminate
201: photosensitive resin composition layer (cured film)
203: metal layer

Claims (14)

A photosensitive resin composition layer forming step in which a photosensitive resin composition is applied to a substrate to form a layer,
An exposure process of exposing the photosensitive resin composition layer applied to the substrate, and
A developing treatment step of performing a development treatment on the exposed photosensitive resin composition layer; and
A curing step of curing the photosensitive resin composition layer after the development,
Including performing a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer after the curing step by vapor phase film formation in the above order,
The temperature of the photosensitive resin composition layer after the curing step when forming the metal layer is less than the glass transition temperature of the photosensitive resin composition layer after the curing step,
A method for producing a laminate in which the photosensitive resin composition has a crosslinked structure formed by exposure to lower solubility in an organic solvent. The method according to claim 1,
The method for manufacturing a laminate, further comprising performing the photosensitive resin composition layer forming step, the exposure step, the developing treatment step, the curing step, and the metal layer forming step in the above order again. delete The method according to claim 1 or 2,
The method for producing a laminate, wherein the photosensitive resin composition contains at least one type of resin selected from a polyimide precursor, a polyimide, a polybenzoxazole precursor, and a polybenzoxazole. The method according to claim 1 or 2,
A method for manufacturing a laminate, further comprising a second metal layer forming step of forming a second metal layer on the surface of the metal layer. The method of claim 5,
The method for manufacturing a laminate, wherein the second metal layer contains copper. The method according to claim 1 or 2,
The method for producing a laminate, wherein the metal layer contains at least one of titanium, tantalum, and copper, and a compound containing at least one of them. The method according to claim 1 or 2,
The method of manufacturing a laminate, wherein the thickness of the metal layer formed by the metal layer forming process is 50 to 2000 nm. The method according to claim 1 or 2,
The method for producing a laminate, wherein the residual stress measured by the laser measurement method of the photosensitive resin composition after the curing step is less than 35 MPa. The method according to claim 1 or 2,
The photosensitive resin composition is for negative-type development, a method for producing a laminate. The method according to claim 1 or 2,
The curing step includes a temperature raising step of raising the temperature of the photosensitive resin composition layer, and a holding step of maintaining the same holding temperature as the final temperature reached in the temperature raising step,
The method for producing a laminate, wherein the holding temperature in the holding step is 250°C or less. The method according to claim 1 or 2,
A method for producing a laminate, wherein the temperature of the photosensitive resin composition layer when forming the metal layer is 30°C or more lower than the glass transition temperature of the photosensitive resin composition layer. A method for manufacturing a semiconductor element, including the method for manufacturing a laminate according to claim 1 or 2. delete

Images