JP7056320B2 - Photosensitive resin composition, resin film and electronic device - Google Patents

Description

The present invention relates to a photosensitive resin composition, a resin film and an electronic device.

In the field of photosensitive resin compositions, various techniques have been developed for the purpose of uniformly coating a transparent substrate with a uniform film thickness by a method such as a slit coater. Examples of this type of technique include the techniques described in Patent Document 1.
According to Patent Document 1, it is described that a uniform coating can be realized by containing a non-volatile component having a specific content and three or more kinds of solvents having a specific boiling point in the photosensitive composition.

Japanese Unexamined Patent Publication No. 2004-354601

In recent years, a technique for collectively manufacturing an electronic device using a "panel-shaped substrate" larger than a normal wafer (for example, a 12-inch wafer) used for a wafer level package has been actively studied. This panel-shaped substrate is also called a "panel level package" and is being actively studied from the viewpoint of improving the manufacturing efficiency of electronic devices.
The present inventor has studied the use of the photosensitive resin composition described in Patent Document 1 for resin films such as permanent films and resist films for panel-level packages. As a result, when the photosensitive resin composition described in Patent Document 1 is applied to the substrate of the panel level package to form a resin film, the thickness of the resin film is not uniform, and further, the edge of the resin film is covered. It was confirmed that sagging (deficiency) occurred.
Therefore, in the present invention, when creating a panel level package, uniformity is improved when an interlayer insulating film, a surface protective film, a permanent film such as a dam material, or a resin film such as a resist film is used, and the edge portion is formed. Provided is a photosensitive resin composition capable of suppressing the occurrence of sagging.

The present inventor has investigated a method for improving the uniformity of the resin film and suppressing the occurrence of sagging at the edge portion when creating a panel level package.
The present inventor has focused on the fact that a wide variety of materials exist on the surface of the substrate of a panel-level package, unlike the substrate of a conventional package. The present inventor has investigated compatibility between a wide variety of substrate materials and photosensitive resin compositions. As a result, it was found that the uniformity of the resin film can be improved and the sagging of the edge portion can be suppressed by satisfying a specific contact angle value.
Based on this finding, the present inventor newly designed a photosensitive resin composition in which the contact angle of the photosensitive resin composition with respect to various substrates is within a specific numerical range, thereby making the thickness of the resin film uniform. We have found that it is possible to realize a photosensitive resin composition that can improve coatability such as sagging of an edge portion, and completed the present invention.

According to the present invention
A photosensitive resin composition used to form a permanent film or a resist film for a panel level package.
Contains an alkali-soluble resin, a photosensitive agent, and a solvent,
The difference θ _max −θ _min between the maximum value θ _max of the contact angle and the minimum value θ _min of the contact angle measured according to the following measurement condition 1 is 40 ° or less.
Provided is a photosensitive resin composition having an average value θ _ave of contact angles of the photosensitive resin composition measured according to the following measurement condition 1 of 10 to 30 °.

(Measurement condition 1)
The photosensitive resin composition was viscous-adjusted with γ-butyrolactone by an E-type viscometer at a rotation frequency of 100 rpm, a temperature of 25 ° C, and a viscosity measured after rotation for 300 seconds at 50 mPa · s, and the temperature was 25 ° C. Then, 2 μL is dropped on each of the following substrates. Regarding the contact angles θ _CCL , θ _Cu , θ _Al , θ _SiN and θ _Si measured for each substrate 10 seconds after dropping, the maximum is θ _max , the minimum is θ _min , and the average value is θ _ave . do.
(substrate)
As the substrate, plated copper whose surface has been washed with a 5 wt% sulfuric acid aqueous solution, a substrate having a spattered Cu as a surface layer, a substrate having a sputtered Al as a surface layer, a substrate having a silicon nitride CVD film as a surface layer, and a bare silicon wafer are used. The correspondence between the substrate and the contact angle is as follows.
-The contact angle when using plated copper whose surface has been washed with a 5 wt% sulfuric acid aqueous solution is defined as θ _CCL .
-The contact angle when a substrate having spattered Cu as the surface layer is used as the substrate is set to θ _Cu .
-The contact angle when a substrate having spatter Al as the surface layer is used as the substrate is θ _Al .
-The contact angle when a substrate having a silicon nitride CVD film as a surface layer is used as the substrate is set to θ _SiN .
-The contact angle when a bare silicon wafer is used as the substrate is θ _Si .

Further, according to the present invention,
A resin film obtained by curing the photosensitive resin composition is provided.

Further, according to the present invention,
An electronic device including the above resin film is provided.

INDUSTRIAL APPLICABILITY The present invention improves uniformity when a panel-level package is formed as an interlayer insulating film, a surface protective film, a permanent film such as a dam material, or a resin film such as a resist film, and sagging occurs at the edge portion. Provided is a photosensitive resin composition capable of suppressing the above-mentioned effects.

Hereinafter, this embodiment will be described.
Unless otherwise specified, the notation "a to b" in the description of the numerical range indicates a or more and b or less. For example, "1 to 5% by mass" means "1% by mass or more and 5% by mass or less".

The photosensitive resin composition according to the present embodiment is a photosensitive resin composition used for forming a permanent film or a resist film for a panel level package, and comprises an alkali-soluble resin, a photosensitive agent, and a solvent. The difference θ _max −θ _min between the maximum value θ _max of the contact angle of the photosensitive resin composition and the minimum value θ _min of the contact angle measured according to the following measurement conditions is 40 ° or less, and is described below. The average value θ _ave of the contact angles of the photosensitive resin composition measured according to the measurement condition 1 is 10 to 30 °.

(Measurement condition 1)
The photosensitive resin composition was viscous-adjusted with γ-butyrolactone by an E-type viscometer at a rotation frequency of 100 rpm, a temperature of 25 ° C, and a viscosity measured after rotation for 300 seconds at 50 mPa · s, and the temperature was 25 ° C. Then, 2 μL is dropped on each of the following substrates. Regarding the contact angles θ _CCL , θ _Cu , θ _Al , θ _SiN and θ _Si measured for each substrate 10 seconds after dropping, the maximum is θ _max , the minimum is θ _min , and the average value is θ _ave . do.

(substrate)
As the substrate, plated copper whose surface has been washed with a 5 wt% sulfuric acid aqueous solution, a substrate having a spattered Cu as a surface layer, a substrate having a sputtered Al as a surface layer, a substrate having a silicon nitride CVD film as a surface layer, and a bare silicon wafer are used. The correspondence between the substrate and the contact angle is as follows.
-The contact angle when plated copper is used as the substrate is θ _CCL .
-The contact angle when a substrate having spattered Cu as the surface layer is used as the substrate is set to θ _Cu .
-The contact angle when a substrate having spatter Al as the surface layer is used as the substrate is θ _Al .
-The contact angle when a substrate having a silicon nitride CVD film as a surface layer is used as the substrate is set to θ _SiN .
-The contact angle when a bare silicon wafer is used as the substrate is θ _Si .

In the field of electronic devices, a packaging technique called panel level packaging (PLP) has been developed in recent years. The panel level package is a package manufactured in a batch using a panel-shaped substrate larger than the wafer used for the wafer level package.

The present inventor has studied the use of conventional photosensitive resin compositions for resin films such as permanent films and resist films for panel-level packages. However, with the conventional photosensitive resin composition, it is difficult to form the thickness of the resin film uniformly, and there is a disadvantage that sagging (deficiency) occurs at the edge of the resin film. Therefore, the present inventor has studied a panel-level package substrate in order to prevent such inconvenience.
In the study, the present inventor found that the surface of the substrate of the panel level package is a copper-clad laminate for forming a conductor circuit pattern or for rust-preventing treatment, unlike the substrate used for the conventional package. Copper foil and copper formed by spatter; Pads made of aluminum; Passivation on chips made of silicon nitride, etc .; Chips made of silicon, etc .; Epoxy resin that seals each member such as chips. We focused on the existence of a wide variety of materials such as encapsulants.

Therefore, the present inventor has described that the difference θ _max −θ _min between the maximum value θ _max of the contact angle with respect to various substrates (5 types) and the minimum value θ _min of the contact angle is equal to or less than a specific value. In addition, a photosensitive resin composition in which the average value θ _ave of the five contact angles is within a specific numerical range has been newly designed. As a result, it was found that the uniformity of the thickness of the resin film can be improved and the occurrence of sagging at the edge portion can be suppressed.

The detailed mechanism is not clear, but the reason for this is presumed as follows.
Conventional photosensitive resin compositions are not compatible with all of the wide variety of materials present on the surface of panel-level packages. Then, in the process of manufacturing the panel level package, there is a material that repels the photosensitive resin composition when the resin layer is formed by a method such as slit coating. However, in the photosensitive resin composition according to the present embodiment, the above θ _max −θ _min is within a specific numerical range, and θ _ave is within a specific numerical range, so that the substrate surface of the panel level package is available. It is presumed that the compatibility with a wide variety of materials existing in is improved (and / or the compatibility with a wide variety of materials is averaged). As a result, even if the photosensitive resin composition is slit-coated, the photosensitive resin composition is not largely repelled, and a resin film having a uniform thickness and capable of suppressing sagging of the edge portion can be formed.

From the above, the photosensitive resin composition according to the present embodiment is a permanent film such as an interlayer insulating film, a surface protective film, a dam material, or a resin film (non-permanent film) such as a resist film when a panel level package is prepared. In this case, the uniformity of the film can be improved and the occurrence of sagging at the edge portion can be suppressed.

(Photosensitive resin composition)
A method for measuring the contact angle of the photosensitive resin composition according to the present embodiment will be described.
As the substrate for measuring the contact angle, plated copper whose surface is washed with a 5 wt% sulfuric acid aqueous solution, a substrate having a sputtered Cu as a surface layer, a substrate having a sputtered Al as a surface layer, a substrate having a silicon nitride CVD film as a surface layer, and bare silicon. Use a wafer.
Further, as the substrate for measuring the contact angle, a substrate having a film thickness of 10 μm formed by the photosensitive resin composition itself according to the present embodiment as a surface layer can also be used.

Here, the correspondence between the substrate and the contact angle is as follows.
-The contact angle when using plated copper whose surface has been washed with a 5 wt% sulfuric acid aqueous solution is defined as θ _CCL .
-The contact angle when a substrate having spattered Cu as the surface layer is used as the substrate is set to θ _Cu .
-The contact angle when a substrate having spatter Al as the surface layer is used as the substrate is θ _Al .
-The contact angle when a substrate having a silicon nitride CVD film as a surface layer is used as the substrate is set to θ _SiN .
-The contact angle when a bare silicon wafer is used as the substrate is θ _Si .
The contact angle when a substrate having a film thickness of 10 μm as the surface layer, which is formed by the photosensitive resin composition itself according to the present embodiment, is used as the substrate is defined as θ _PSPI .

The contact angle is measured for these substrates. The contact angle is measured by dropping 2 μL of the photosensitive resin composition according to the present embodiment whose viscosity is adjusted with γ-butyrolactone so that the viscosity is 50 mPa · s at a temperature of 25 ° C. The "viscosity" here is a viscosity measured by an E-type viscometer at a rotation frequency of 100 rpm, a temperature of 25 ° C., and after rotation for 300 seconds.
As the contact angle, a value for each substrate measured 10 seconds after dropping is adopted.
The reason for adjusting the viscosity of the dropping photosensitive resin composition in the measurement of the contact angle is that the contact angle varies depending on the viscosity of the photosensitive resin composition. This is to align. If the viscosity of the photosensitive resin composition of the present embodiment is exactly 50 mPa · s without adjusting the viscosity, the viscosity adjustment is unnecessary.
In the present embodiment, the maximum values of θ _CCL , θ _PPI , θ _Cu , θ _Al , θ _SiN and θ _Si are θ _max , the minimum value is θ _min , the mean value is θ _ave , and the standard deviation is θ _st . And.

The upper limit of the difference θ _max −θ _min from the minimum value θ _min of the contact angle of the photosensitive resin composition according to the present embodiment is 40 ° or less, preferably 38 ° or less, and more preferably 35 ° or less. Is more preferable. This makes it possible to more uniformly control the affinity of the photosensitive resin composition for a wide variety of materials present on the substrate of the panel level package. Further, this makes it possible to prevent the photosensitive resin composition from being repelled by the substrate when the photosensitive resin composition is applied using the slit coat. Therefore, the thickness of the resin film can be made uniform, and the sagging of the edge portion can be suppressed.
Basically, the smaller θ _max −θ _min is, the more uniformly the resin film can be formed. However, the lower limit of θ _max −θ _min may be, for example, 0 ° or more, 1 ° or more, or 2 ° or more. But it may be.

The upper limit of the maximum value θ _max of the contact angle of the photosensitive resin composition according to the present embodiment is, for example, preferably 50 ° or less, more preferably 48 ° or less, and 45 ° or less. Is even more preferable. As a result, it is possible to further suppress the photosensitive resin composition from being repelled by various members existing on the substrate of the panel level package. Therefore, the thickness of the resin film can be made uniform, and the sagging of the edge portion can be suppressed.
The lower limit of θ _max may be, for example, 25 ° or more, 30 ° or more, or 35 ° or more.

The lower limit of the minimum contact angle θ _min of the photosensitive resin composition according to the present embodiment is, for example, preferably 3 ° or more, and more preferably 5 ° or more. As a result, it is possible to prevent the photosensitive resin composition from spreading too much on the substrate of the panel level package and overflowing from the substrate.
The upper limit of θ _min may be, for example, 15 ° or less, 12 ° or less, or 10 ° or less.

The upper limit of the average value θ _ave of the contact angle of the photosensitive resin composition according to the present embodiment is 30 ° or less, preferably 28 ° or less, and more preferably 25 ° or less. .. As a result, it is possible to prevent the photosensitive resin composition from being repelled by various members existing on the substrate of the panel level package. Therefore, the thickness of the resin film can be made uniform, and the sagging of the edge portion can be suppressed.
The lower limit of θ- _ave is 10 ° or more, preferably 15 ° or more, and more preferably 20 ° or more. As a result, it is possible to prevent the photosensitive resin composition from spreading too much on the substrate of the panel level package and overflowing from the substrate.

The upper limit of the standard deviation θ _st of the contact angle of the photosensitive resin composition according to the present embodiment is, for example, preferably 25 ° or less, more preferably 22 ° or less, and more preferably 20 ° or less. Is even more preferable. As a result, it is possible to reduce the variation in the affinity of the photosensitive resin composition with various members such as CCL, PSPI, Cu, Al, silicon nitride, and Si existing on the substrate of the panel level package. Therefore, the thickness of the resin film can be made uniform and the sagging of the edge portion can be suppressed.
The lower limit of θ _st may be, for example, 1 ° or more, 5 ° or more, or 10 ° or more.

As a precaution, the typical numerical ranges for each of θ _CCL , θ _Cu , θ _Al , θ _SiN , and θ _Si are as follows: θ _CCL : 15 to 50 ° as an example, specifically Is 20-45 °
θ _Cu : 15 to 50 ° as an example, specifically 20 to 45 °
θ _Al : 3 to 30 ° as an example, specifically 5 to 25 °
θ _SiN : 3 to 25 ° as an example, specifically 5 to 20 °
θ _Si : 3 to 25 ° as an example, specifically 5 to 20 °

In the present embodiment, for example, by appropriately setting the preparation method and compounding composition of the photosensitive resin composition, the above-mentioned θ _CCL , θ _Cu , θ _Al , θ Si _N and θ _Si are set within a suitable numerical range. It is possible to control θ _max , θ _min , θ _ave and θ _st . Among these, specifically, the step of producing the photosensitive resin composition which is a varnish is performed in a nitrogen atmosphere; the varnish does not go through the step of completely volatilizing the solvent from the alkali-soluble resin to dry it. To prepare a photosensitive resin composition that is; to control the solvent ratio in the mixed solvent; It is mentioned as an important factor controlling _max -θ _min and θ _ave . Although the detailed mechanism is not clear, it is presumed that this can improve the dispersibility of the alkali-soluble resin in the photosensitive resin composition and reduce the variation in the contact angle with respect to a wide variety of materials. Therefore, θ _max −θ _min can be reduced, and θ _ave can be set within a desired numerical range.

In the panel level package process, there may be a case where the photosensitive resin composition is further formed on the film formed of the photosensitive resin composition. Therefore, it is preferable that the contact angle with respect to the film formed of the photosensitive resin composition is also an appropriate value.
Specifically, for a substrate having a film having a film thickness of 10 μm formed by the photosensitive resin composition of the present embodiment as a surface layer, when the contact angle measured according to the above-mentioned measurement condition 1 is θ _PSPI , θ _PSPI is It is preferably 10 to 30 °.
More specifically, the upper limit of θ _PSPI is preferably 28 ° or less, and more preferably 25 ° or less. Further, the lower limit of θ _PSPI is preferably 10 ° or more, and more preferably 15 ° or more.

Next, the components contained in the photosensitive resin composition according to the present embodiment will be described.
The photosensitive resin composition according to the present embodiment contains an alkali-soluble resin, a photosensitive agent, and a solvent.

(Alkali-soluble resin)
The alkali-soluble resin is not limited, and can be selected according to physical properties such as mechanical properties and optical properties required for the resin film. Specific examples of the alkali-soluble resin include polyamide resin, polybenzoxazole resin, polyimide resin, phenol resin, hydroxystyrene resin, and cyclic olefin resin. As the alkali-soluble resin, one or a combination of two or more of the above specific examples can be used. As the alkali-soluble resin, for example, a polyamide resin or a polybenzoxazole resin is preferably used, and more preferably a polybenzoxazole resin is used among the above specific examples. This makes it possible to improve the dispersibility of the alkali-soluble resin in the photosensitive resin composition. Further, it is also preferable from the viewpoint that the uniformity of the film thickness can be improved and the occurrence of defects can be suppressed by improving the physical properties such as the mechanical strength of the resin film made of the photosensitive resin composition.

(Polyamide resin, polybenzoxazole resin)
As the polyamide resin, for example, it is preferable to use an aromatic polyamide containing an aromatic ring as the structural unit of the polyamide, and it is more preferable to use a polyamide resin containing a structural unit represented by the following formula (PA1). This makes it possible to improve physical properties such as the mechanical strength of the resin film made of the photosensitive resin composition. Therefore, it is also preferable from the viewpoint of improving the uniformity of the film thickness and suppressing the occurrence of defects.
In the present embodiment, the aromatic ring means a benzene ring; a fused aromatic ring such as a naphthalene ring, an anthracene ring, or a pyrene ring; a complex aromatic ring such as a pyridine ring or a pyrrole ring. The polyamide resin of the present embodiment preferably contains a benzene ring as an aromatic ring from the viewpoint of mechanical strength and the like.

The polyamide resin containing the structural unit represented by the above formula (PA1) is a precursor of the polybenzoxazole resin. The polyamide resin containing the structural unit represented by the above formula (PA1) is dehydrated and ring-closed by being heat-treated at a temperature of 150 ° C. or higher and 380 ° C. or lower under the conditions of 30 minutes or longer and 50 hours or lower, and polybenzo. It can be an oxazole resin. Here, the structural unit of the above formula (PA1) becomes the structural unit represented by the following formula (PBO1) by dehydration ring closure.
When the alkali-soluble resin according to the present embodiment is a polyamide resin containing a structural unit represented by the above formula (PA1), for example, the photosensitive resin composition is dehydrated and ring-closed by the above heat treatment to form a polybenzoxazole resin. May be. That is, the photosensitive resin composition subjected to the above heat treatment contains a polybenzoxazole resin which is an alkali-soluble resin.
When the alkali-soluble resin is a polyamide resin containing a structural unit represented by the above formula (PA1), a resin film and an electronic device to be described later are produced, and then the heat treatment is performed to dehydrate and close the ring to polybenzo. It may be an oxazole resin. When a polybenzoxazole resin is obtained by dehydrating and ring-opening a polyamide resin, mechanical properties and thermal properties can be improved. This is convenient from the viewpoint that deformation of the resin film can be suppressed.

(Polyamide resin, polyimide resin)
Further, as the polyamide resin, for example, a resin containing a structural unit represented by the following general formula (PA2) may be used.
The polyamide resin containing the structural unit represented by the following general formula (PA2) is a precursor of the polyimide resin. The polyamide resin containing the structural unit represented by the following general formula (PA2) is dehydrated and ring-closed by being heat-treated at a temperature of 150 ° C. or higher and 380 ° C. or lower under the conditions of 30 minutes or longer and 50 hours or lower, and is made of polyimide. It can be a resin. Here, the structural unit of the following formula (PA2) becomes the structural unit represented by the following formula (PI1) by dehydration ring closure.
When the alkali-soluble resin according to the present embodiment is a polyamide resin containing a structural unit represented by the following formula (PA2), the photosensitive resin composition may be dehydrated and ring-closed by the above heat treatment to obtain a polyimide resin. That is, the photosensitive resin composition subjected to the above heat treatment contains a polyimide resin which is an alkali-soluble resin.
When the alkali-soluble resin is a polyamide resin containing a structural unit represented by the following formula (PA2), the polyimide resin is dehydrated and closed by the above heat treatment after producing a resin film and an electronic device to be described later. May be.

In the general formula ( ^PA2 ), RB and ^RC are independently organic groups having 1 or more and 30 or less carbon atoms.

In the general formula ( ^PI1 ), RB and ^RC are the same as those in the general formula (PA2).

As the ^RB and ^RC in the general formula (PA2) and the general formula (PI1), specifically, an organic group having an aromatic ring is preferable.
As the organic group having an aromatic ring, specifically, one containing a benzene ring, a naphthalene ring or an anthracene ring is preferable, and one containing a benzene ring is more preferable. This makes it possible to improve the dispersibility of the alkali-soluble resin and keep the contact angle with respect to various materials within a desired numerical range.

(Manufacturing method of polyamide resin)
The polyamide resin according to this embodiment is polymerized as follows, for example.
First, the polyamide is polymerized by polycondensing the diamine monomer and the dicarboxylic acid monomer in the polymerization step (S1). Next, the low molecular weight component is removed by the low molecular weight component removing step (S2) to obtain a polyamide resin containing polyamide as a main component.

(Polymerization step (S1))
In the polymerization step (S1), the diamine monomer and the dicarboxylic acid monomer are polycondensed. The method of polycondensation for polymerizing a polyamide is not limited, and specific examples thereof include melt polycondensation, acid chloride method, and direct polycondensation.
Instead of the dicarboxylic acid monomer, a compound selected from the group consisting of tetracarboxylic acid dianhydride, trimellitic acid anhydride, dicarboxylic acid dichloride or active ester type dicarboxylic acid may be used. Specific examples of the method for obtaining the active ester-type dicarboxylic acid include a method in which the dicarboxylic acid is reacted with 1-hydroxy-1,2,3-benzotriazole or the like.

The diamine monomer used for the polymerization of the polyamide resin and the dicarboxylic acid monomer will be described below. As the diamine monomer and the dicarboxylic acid monomer, only one kind may be used, or two or more kinds of diamine monomers and / or two or more kinds of dicarboxylic acid monomers may be used.

(Diamine monomer)
The diamine monomer used for the polymerization is not limited, and for example, it is preferable to use a diamine monomer having an aromatic ring in the structure, and it is more preferable to use a diamine monomer having a phenolic hydroxyl group in the structure. By producing a polyamide resin using such a diamine monomer as a raw material, the conformation of the polyamide resin can be controlled, and the dispersibility of the composition can be further improved.

Here, as the diamine monomer containing a phenolic hydroxyl group in the structure, for example, a diamine monomer represented by the following general formula (DA1) is preferable. By producing the polyamide resin from such a diamine monomer as a raw material, the conformation of the polyamide resin can be controlled, and the molecular chains of the polyamide resin can form a tighter structure. Therefore, it is considered that the molecular structure can be frozen and the adhesion to the substrate can be improved by the coordination in which the molecules of the alkali-soluble resin and the metal molecules are more strongly bound.
In addition, for example, when the diamine monomer represented by the following general formula (DA1) is used, the polyamide resin contains a structural unit represented by the following general formula (PA2). That is, the polyamide resin according to this embodiment preferably contains, for example, a structural unit represented by the following general formula (PA2).

In the general formula (DA1), R ⁴ is one selected from the group consisting of hydrogen atom, carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, silicon atom, chlorine atom, fluorine atom and bromine atom. It is a group formed by two or more kinds of atoms. R ⁵ to R ¹⁰ independently represent hydrogen or an organic group having 1 or more and 30 or less carbon atoms.

^In the general formula (PA2), ^R4 , R5 to R10 are the ^same as the above general formula (DA1).

^R4 in the general formulas (DA1) and (PA2) is selected from the group consisting of hydrogen atom, carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, silicon atom, chlorine atom, fluorine atom and bromine atom. A group formed by one or more atoms.
^R4 is a divalent group. Here, the divalent group indicates a valence. That is, it shows that R ⁴ has two bonds to bond with other atoms.

When R ⁴ in the general formulas (DA1) and (PA2) contains a carbon atom, R ⁴ is, for example, a group having 1 or more and 30 or less carbon atoms, preferably a group having 1 or more and 10 or less carbon atoms, preferably carbon. It is more preferably a group having a number of 1 or more and 5 or less, and further preferably a group having 1 or more and 3 or less carbon atoms.

When R ⁴ in the general formulas (DA1) and (PA2) contains a carbon atom, specific examples of R ⁴ include an alkylene group, an arylene group, a halogen-substituted alkylene group, and a halogen-substituted arylene group.
The alkylene group may be, for example, a linear alkylene group or a branched chain alkylene group. Specific examples of the linear alkylene group include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decanylene group, trimethylene group and tetramethylene group. , Pentamethylene group, hexamethylene group and the like. Specific examples of the branched alkylene group include -C (CH ₃ ) _2- , -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, and -C (CH ₃ ) (CH ₂ ). Alkylmethylene groups such as CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _2- ; -CH (CH ₃ ) CH _2- , -CH ( Alkylethylene such as CH ₃ ) CH (CH ₃ )-, -C (CH ₃ ) ₂ CH _2- , -CH (CH ₂ CH ₃ ) CH _2- , -C (CH ₂ CH ₃ ) ₂ -CH _2- The group etc. can be mentioned.
Specific examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, and a group in which two or more arylene groups are bonded to each other.
As the halogen-substituted alkylene group and the halogen-substituted arylene group, specifically, those in which the hydrogen atom in the above-mentioned alkylene group and arylene group is substituted with a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom are used. Can be done. Among these, those in which a hydrogen atom is replaced with a fluorine atom are preferable.

When R ⁴ in the general formulas (DA1) and (PA2) does not contain a carbon atom, the R ⁴ specifically includes a group consisting of an oxygen atom or a sulfur atom.

R ⁵ -R ¹⁰ in the general formulas (DA1) and (PA2) are independently hydrogen or an organic group having 1 or more and 30 or less carbon atoms, and are, for example, hydrogen or an organic group having 1 or more and 10 or less carbon atoms. It is preferably hydrogen or an organic group having 1 or more and 5 or less carbon atoms, further preferably hydrogen or an organic group having 1 or more and 3 or less carbon atoms, and hydrogen or an organic group having 1 or more carbon atoms and 2 or less carbon atoms. It is more preferably an organic group. As a result, the aromatic rings of the polyamide resin can be closely arranged. Therefore, the molecular structure can be frozen and the adhesion can be improved by the coordination in which the molecules of the alkali-soluble resin and the metal molecules are more strongly bound.

Specific examples of the organic group having 1 or more and 30 or less carbon atoms of R5 ^- R10 in the general formulas (DA1) and (PA2) include a methyl group, an ethyl group, an n ^- propyl group, an isopropyl group and an n-butyl group. Alkyl groups such as isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group; alkenyl group such as allyl group, pentenyl group and vinyl group. Alkinyl group such as ethynyl group; Alkylidene group such as methylidene group and ethylidene group; Aryl group such as tolyl group, xsilyl group, phenyl group, naphthyl group and anthrasenyl group; Aralkyl group such as benzyl group and phenethyl group; Adamantyl group, Cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cyclooctyl group; alkalinel groups such as tolyl group and xsilyl group can be mentioned.

Specific examples of the diamine monomer represented by the general formula (DA1) include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4'-methylenebis (2-amino-3). , 6dimethylphenol), 4,4'-methylenebis (2-aminophenol), 1,1-bis (3-amino4-hydroxyphenyl) ethane, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, etc. Can be mentioned. By using these diamine monomers, the aromatic rings of the polyamide resin can be closely arranged. Therefore, the molecular structure can be frozen and the adhesion can be improved by the coordination in which the molecules of the alkali-soluble resin and the metal molecules are more strongly bound. As the diamine monomer, one or a combination of two or more of the above specific examples can be used.
The structural formulas of these diamine monomers are shown below.

(Dicarboxylic acid monomer)
The dicarboxylic acid monomer used for the polymerization is not limited, and for example, it is preferable to use a dicarboxylic acid monomer containing an aromatic ring in the structure.
As the dicarboxylic acid monomer containing an aromatic ring, for example, those represented by the following general formula (DC1) are preferably used. By producing the polyamide resin from such a dicarboxylic acid monomer as a raw material, the conformation of the polyamide resin can be controlled and the dispersibility in the mixed solvent can be improved. Then, by improving the dispersibility, it becomes easy to control the value of θ _max −θ _min and the value of θ _ave to a desired value.

In the general formula (DC1), R ¹¹ is one selected from the group consisting of hydrogen atom, carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, silicon atom, chlorine atom, fluorine atom and bromine atom. It is a group formed by two or more kinds of atoms. R ¹² to R ¹⁹ independently represent hydrogen or an organic group having 1 or more and 30 or less carbon atoms.

In addition, for example, when the dicarboxylic acid monomer represented by the following general formula (DC1) is used, the polyamide resin typically contains a structural unit represented by the following general formula (PA3). In the general formula (PA3), the definitions of R ¹¹ and R ¹² to R ¹⁹ are the same as those in the general formula (DC1).

R ¹¹ in the general formulas (DC1) and (PA3) is selected from the group consisting of hydrogen atom, carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, silicon atom, chlorine atom, fluorine atom and bromine atom. A group formed by one or more atoms.
R ¹¹ is a divalent group. Here, the divalent group indicates a valence. That is, it shows that R ¹¹ has two bonds to bond with other atoms.

When R ¹¹ in the general formulas (DC1) and (PA3) contains a carbon atom, R ¹¹ is, for example, a group having 1 or more and 30 or less carbon atoms, preferably a group having 1 or more and 10 or less carbon atoms, preferably carbon. It is more preferably a group having a number of 1 or more and 5 or less, and further preferably a group having 1 or more and 3 or less carbon atoms.

When R ¹¹ in the general formulas (DC1) and (PA3) contains a carbon atom, specific examples of R ¹¹ include an alkylene group, an arylene group, a halogen-substituted alkylene group, and a halogen-substituted arylene group.
The alkylene group may be, for example, a linear alkylene group or a branched chain alkylene group. Specific examples of the linear alkylene group include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decanylene group, trimethylene group and tetramethylene group. , Pentamethylene group, hexamethylene group and the like. Specific examples of the branched alkylene group include -C (CH ₃ ) _2- , -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, and -C (CH ₃ ) (CH ₂ ). Alkylmethylene groups such as CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _2- ; -CH (CH ₃ ) CH _2- , -CH ( Alkylethylene such as CH ₃ ) CH (CH ₃ )-, -C (CH ₃ ) ₂ CH _2- , -CH (CH ₂ CH ₃ ) CH _2- , -C (CH ₂ CH ₃ ) ₂ -CH _2- The group etc. can be mentioned.
Specific examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, and a group in which two or more arylene groups are bonded to each other.
As the halogen-substituted alkylene group and the halogen-substituted arylene group, specifically, those in which the hydrogen atom in the above-mentioned alkylene group and arylene group is substituted with a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom are used. Can be done. Among these, those in which a hydrogen atom is replaced with a fluorine atom are preferable.

When R ¹¹ in the general formulas (DC1) and (PA3) does not contain a carbon atom, the R ¹¹ specifically includes a group composed of an oxygen atom or a sulfur atom.

R ¹² to R ¹⁹ in the general formulas (DC1) and (PA3) are independently hydrogen or an organic group having 1 or more and 30 or less carbon atoms, and are, for example, hydrogen or an organic group having 1 or more and 10 or less carbon atoms. It is preferably hydrogen or an organic group having 1 or more and 5 or less carbon atoms, more preferably hydrogen or an organic group having 1 or more and 3 or less carbon atoms, and even more preferably hydrogen.

Specific examples of the organic group having 1 or more and 30 or less carbon atoms of ^R12 - ^R19 in the general formulas (DC1) and (PA3) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group. Alkyl groups such as isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group; alkenyl group such as allyl group, pentenyl group and vinyl group. Alkinyl group such as ethynyl group; Alkylidene group such as methylidene group and ethylidene group; Aryl group such as tolyl group, xsilyl group, phenyl group, naphthyl group and anthrasenyl group; Aralkyl group such as benzyl group and phenethyl group; Adamantyl group, Cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cyclooctyl group; alkalinel groups such as tolyl group and xsilyl group can be mentioned.

As the dicarboxylic acid monomer, specifically, diphenyl ether 4,4'-dicarboxylic acid, isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid and the like can be used. As the dicarboxylic acid monomer, among the above specific examples, it is preferable to use diphenyl ether 4,4'-dicarboxylic acid or isophthalic acid, and it is more preferable to use diphenyl ether 4,4'-dicarboxylic acid. The aromatic rings of the polyamide resin can be closely arranged. Therefore, the molecular structure can be frozen and the adhesion can be improved by the coordination in which the molecules of the alkali-soluble resin and the metal molecules are more strongly bound.

It is preferable to modify the amino group present at the terminal of the polyamide resin at the same time as the polymerization step (S1) or after the polymerization step (S1). The modification can be carried out, for example, by reacting a diamine monomer or a polyamide resin with a specific acid anhydride or a specific monocarboxylic acid. Therefore, it is preferable that the polyamide resin according to the present embodiment has an amino group at the terminal modified with a specific acid anhydride or a specific monocarboxylic acid. The specific acid anhydride and the specific monocarboxylic acid have one or more functional groups consisting of a group consisting of an alkenyl group, an alkynyl group, and a hydroxyl group. Further, as the specific acid anhydride and the specific monocarboxylic acid, for example, those containing a nitrogen atom are preferable. This makes it possible to improve the adhesion between the photosensitive resin composition after post-baking and a metal such as Al or Cu.

Specific examples of the specific acid anhydride include maleic acid anhydride, citraconic acid anhydride, 2,3-dimethylmaleic acid anhydride, 4-cyclohexene-1,2-dicarboxylic acid anhydride, and exo-3. , 6-Epoxy-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, methyl-5-norbornen-2,3-dicarboxylic acid anhydride, itaconic acid anhydride Examples thereof include anhydrate, 4-ethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, 4-hydroxyphthalic anhydride and the like. As the specific acid anhydride, one or a combination of two or more of the above specific examples can be used.

When the amino group existing at the end of the polyamide resin is modified with a specific acid anhydride having a ring shape, the specific acid anhydride having a ring shape opens. Here, after modifying the polyamide resin, a structural unit derived from a specific acid anhydride having a ring shape may be closed to form an imide ring. Examples of the ring-closing method include heat treatment.
Specific examples of the specific monocarboxylic acid include 5-norbornene-2-carboxylic acid, 4-hydroxybenzoic acid, and 3-hydroxybenzoic acid. As the specific monocarboxylic acid, one or a combination of two or more of the above specific examples can be used.

Further, the carboxyl group existing at the terminal of the polyamide resin may be modified at the same time as the polymerization step (S1) or after the polymerization step (S1). The modification can be carried out, for example, by reacting a dicarboxylic acid monomer or a polyamide resin with a specific nitrogen atom-containing heteroaromatic compound. Therefore, in the polyamide resin according to the present embodiment, it is preferable that the carboxyl group at the terminal is modified with a specific nitrogen atom-containing heteroaromatic compound. The specific nitrogen atom-containing heteroaromatic compound includes 1- (5-1H-triazoyl) methylamino group, 3- (1H-pyrazoyl) amino group, 4- (1H-pyrazoyl) amino group, and 5-. (1H-pyrazoyl) amino group, 1- (3-1H-pyrazoyl) methylamino group, 1- (4-1H-pyrazoyl) methylamino group, 1- (5-1H-pyrazoyl) methylamino group, (1H- One or more functionalities consisting of a group consisting of a tetrasol-5-yl) amino group, a 1- (1H-tetrazol-5-yl) methyl-amino group and a 3- (1H-tetrazol-5-yl) benz-amino group. It has a group. This makes it possible to increase the number of lone electron pairs in the photosensitive resin composition. Therefore, it is possible to improve the adhesion between the photosensitive resin composition after pre-baking and post-baking and a metal such as Al.
Specific examples of the specific nitrogen atom-containing heteroaromatic compound include 5-aminotetrazole.

(Low molecular weight component removing step (S2))
Following the polymerization step (S1), it is preferable to perform a low molecular weight component removing step (S2) to remove the low molecular weight component.
Specifically, the organic layer containing a mixture of the low molecular weight component and the polyamide resin is concentrated by filtration or the like, and then dissolved again in an organic solvent such as water / isopropanol. As a result, the precipitate can be filtered off to obtain a polyamide resin from which low molecular weight components have been removed.

For the polyamide resin, for example, it is preferable to prepare a photosensitive resin composition which is a varnish without going through a step of completely volatilizing the solvent and becoming dry after the step of removing the low molecular weight component. As a result, it is possible to prevent the dispersibility of the polyamide from being lowered due to the interaction derived from the amide bond between the molecules of the polyamide resin. Therefore, the contact angle with respect to various materials can be kept uniform on the substrate of the panel level package.

(Phenol resin)
Specific examples of the phenol resin include novolak-type phenol resins such as phenol novolac resin, cresol novolak resin, bisphenol novolak resin, and phenol-biphenyl novolak resin; phenols such as novolak-type phenol resin, resol-type phenol resin, and cresol novolak resin. Reaction products of compounds and aldehyde compounds; reaction products of phenol compounds such as phenol aralkyl resins and dimethanol compounds can be mentioned. The phenolic resin may contain one or more of the above specific examples.

The above-mentioned phenol compound used in the reaction product of the phenol compound and the aldehyde compound or the reaction product of the phenol compound and the dimethanol compound is not limited.
Specific examples of such phenol compounds include cresols such as phenol, o-cresol, m-cresol, and p-cresol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, and 2 , 6-Xylenol, 3,4-Xylenol, 3,5-Xylenol and other xylenols; o-ethylphenol, m-ethylphenol, p-ethylphenol and other ethylphenols; isopropylphenol, butylphenol, p-tert- Alkylphenols such as butylphenol; polyhydric phenols such as resorcinol, catechol, hydroquinone, pyrogallol, fluoroglucolcinol; biphenyl-based phenols such as 4,4'-biphenol. As the phenol compound, one or more of the above specific examples can be used.

The aldehyde compound used in the above-mentioned reaction product of the phenol compound and the aldehyde compound is not limited as long as it is a compound having an aldehyde group.
Specific examples of such an aldehyde compound include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, salicylaldehyde and the like. As the aldehyde compound, one or more of the above specific examples can be used.

The above-mentioned dimethanol compound used in the reaction product of the phenol compound and the dimethanol compound is not limited.
Specific examples of such a dimethanol compound include 1,4-benzenedimethanol, 1,3-benzenedimethanol, 4,4'-biphenyldimethanol, 3,4'-biphenyldimethanol, and 3, Dimethanol compounds such as 3'-biphenyldimethanol, 2,6-naphthalenedimethanol, 2,6-bis (hydroxymethyl) -p-cresol; 1,4-bis (methoxymethyl) benzene, 1,3-bis. (Methoxymethyl) benzene, 4,4'-bis (methoxymethyl) biphenyl, 3,4'-bis (methoxymethyl) biphenyl, 3,3'-bis (methoxymethyl) biphenyl, methyl 2,6-naphthalenedicarboxylate , Etc., bis (alkoxymethyl) compounds, or 1,4-bis (chloromethyl) benzene, 1,3-bis (chloromethyl) benzene, 1,4-bis (bromomethyl) benzene, 1,3-bis (bromomethyl) ) Benzene, 4,4'-bis (chloromethyl) biphenyl, 3,4'-bis (chloromethyl) biphenyl, 3,3'-bis (chloromethyl) biphenyl, 4,4'-bis (bromomethyl) biphenyl, Bis (Hargenoalkyl) compounds such as 3,4'-bis (bromomethyl) biphenyl or 3,3'-bis (bromomethyl) biphenyl, 4,4'-bis (methoxymethyl) biphenyl, 4,4'-bis ( Examples thereof include biphenyl aralkyl compounds such as methoxymethyl) biphenyl. As the dimethanol compound, one or more of the above specific examples can be used.

(Hydroxystyrene resin)
The hydroxystyrene resin is not limited, and specifically, a polymerization reaction product or a copolymer obtained by polymerizing or copolymerizing one or more selected from the group consisting of hydroxystyrene, hydroxystyrene derivatives, styrene and styrene derivatives. A polymerization reaction product can be used.
Specific examples of the hydroxystyrene derivative and the styrene derivative include those in which the hydrogen atom contained in the aromatic ring of hydroxystyrene or styrene is replaced with a monovalent organic group. Examples of the monovalent organic group substituting the hydrogen atom include an alkyl group such as a methyl group, an ethyl group and an n-propyl group; an alkenyl group such as an allyl group and a vinyl group; an alkynyl group such as an ethynyl group; a methylidene group. Examples thereof include an alkylidene group such as an ethylidene group; a cycloalkyl group such as a cyclopropyl group; a heterocyclic group such as an epoxy group and an oxetanyl group.

(Cyclic olefin resin)
The cyclic olefin resin is not limited, and specifically, a polymerization reaction product or a copolymerization reaction product obtained by polymerizing or copolymerizing one or more selected from the group consisting of norbornene and norbornene derivatives is used. be able to.
Here, as the norbornene derivative, specifically, norbornene, bicyclo [2.2.1] -hept-2-ene (common name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl- 2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (1-Methyl-4-pentenyl) -2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 2-acetyl-5-norbornene, 5-norbornene- Examples thereof include methyl 2-carboxylate, 5-norbornene-2,3-dicarboxylic acid anhydride and the like.

The lower limit of the content of the alkali-soluble resin in the photosensitive resin composition is preferably 30 parts by mass or more, preferably 40 parts by mass, for example, when the total solid content of the photosensitive resin composition is 100 parts by mass. The above is more preferable, 50 parts by mass or more is further preferable, 60 parts by mass or more is further preferable, and 70 parts by mass or more is particularly preferable. This makes it possible to improve the dispersibility of the alkali-soluble resin in the photosensitive resin composition and keep the contact angle with respect to various materials within a desired numerical range.
Further, the upper limit of the content of the alkali-soluble resin in the photosensitive resin composition is preferably 95 parts by mass or less, for example, when the total solid content of the photosensitive resin composition is 100 parts by mass, 90 parts by mass. It is more preferably parts by mass or less, and even more preferably 85 parts by mass or less.
In the present embodiment, the total solid content of the photosensitive resin composition means the total amount of the components contained in the photosensitive resin composition excluding the solvent.

(Photosensitive agent)
As the photosensitive agent, a photoacid generator that generates an acid by absorbing light energy can be used.
Specific examples of the photoacid generator include diazoquinone compounds; diaryliodonium salts; 2-nitrobenzyl ester compounds; N-iminosulfonate compounds; imidesulfonate compounds; 2,6-bis (trichloromethyl) -1,3. 5-Triazine compounds; examples include dihydropyridine compounds. Among these, it is preferable to use a photosensitive diazoquinone compound. Thereby, the sensitivity of the photosensitive resin composition can be improved. Therefore, the accuracy of the pattern can be improved and the appearance can be improved. The photoacid generator may include one or more of the above specific examples.
When the photosensitive resin composition is of the positive type, a triarylsulfonium salt; an onium salt such as a sulfonium / borate salt may be used in combination as the photosensitive agent. Thereby, the sensitivity of the photosensitive resin composition can be further improved.

In each of the above diazoquinone compounds, Q is a structure represented by the following formula (a), the following formula (b) and the following formula (c), or a hydrogen atom. However, at least one of the Qs of each diazoquinone compound has a structure represented by the following formula (a), the following formula (b) and the following formula (c).
The Q of the diazoquinone compound preferably contains the following formula (a) or the following formula (b). This makes it possible to improve the transparency of the photosensitive resin composition. Therefore, the appearance of the photosensitive resin composition can be improved.

When the alkali-soluble resin is 100 parts by mass, the lower limit of the content of the photosensitive agent in the photosensitive resin composition is, for example, preferably 1 part by mass or more, and more preferably 3 parts by mass or more. It is more preferably 5 parts by mass or more. Thereby, the photosensitive resin composition can exhibit appropriate sensitivity.
Further, the upper limit of the content of the photosensitive agent in the photosensitive resin composition is preferably, for example, 30 parts by mass or less, and 20 parts by mass or less, when the alkali-soluble resin is 100 parts by mass. More preferred. This makes it possible to prevent the photosensitive resin composition from being repelled by the material present on the substrate surface of the panel level package.

(solvent)
As the solvent according to this embodiment, an organic solvent is typically used.
Specifically, N-methyl-2-pyrrolidone (NMP), 3-methoxy-N, N-dimethylpropanamide, N, N-dimethylformamide, N, N-dimethylpropionamide, N, N-diethylacetamide, Amid solvents such as 3-butoxy-N, N-dimethylpropanamide, N, N-dibutylformamide; N, N-dimethylacetamide, tetramethylurea (TMU), 1,3-dimethyl-2-imidazolidinone, Tetrabutylurea, N, N'-dimethylpropylene urea, 1,3-dimethoxy-1,3-dimethylurea, N, N'-diisopropyl-O-methylisourea, O, N, N'-triisopropylisourea, O -Urea solvents such as tert-butyl-N, N'-diisopropylisourea, O-ethyl-N, N'-diisopropylisourea, O-benzyl-N, N'-diisopropylisourea; propylene glycol monomethyl ether ( PGME), propylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, 1,3-butylene glycol Ether solvent such as -3-monomethyl ether; acetate solvent such as propylene glycol monomethyl ether acetate (PGMEA), methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate; tetrahydrofurfuryl alcohol, benzyl Alcohol-based solvents such as alcohol, 2-ethylhexanol, butanediol, isopropyl alcohol; ketone solvents such as cyclopentanone, cyclohexanone, diacetone alcohol, 2-heptanone; γ-butyrolactone (GBL), γ-valerolactone, etc. Lactone-based solvent; carbonate-based solvent such as ethylene carbonate and propylene carbonate; sulfone-based solvent such as dimethyl sulfoxide (DMSO) and sulfolane; ester-based solvent such as methyl pyruvate, ethyl pyruvate and methyl-3-methoxypropionate. ; Aromatic hydrocarbon solvents such as mesitylene, toluene, xylene and the like can be mentioned. As the solvent, one or a combination of two or more of the above specific examples can be used. Among these, a lactone-based solvent is preferable from the viewpoint of coatability and prevention of sagging.

As the solvent, for example, one or more selected from the group consisting of an amide solvent and a urea solvent and one or more selected from the group consisting of an acetate solvent and a lactone solvent are used in combination in the above specific examples. It is preferable to do so. Thereby, the dispersibility of the alkali-soluble resin can be improved. In addition, the affinity for various materials existing on the substrate surface of the panel level package can be improved. Therefore, the contact angle with respect to various materials can be set within a close numerical range, the uniformity of the resin film can be improved, and the sagging of the edge portion can be suppressed.

The total content of the amide-based solvent and the urea-based solvent in the solvent is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and 25 parts by mass or more when the solvent is 100 parts by mass. Is more preferable. This makes it possible to improve the polarity in the mixed solvent. Therefore, the dispersibility of alkali-soluble resins such as polyamide resin, polybenzoxazole resin, and polyimide resin can be improved. From the above, the contact angle for various materials can be set within a desired numerical range.

The photosensitive resin composition according to the present embodiment further contains additives such as an adhesion aid, a thermal cross-linking agent, a surfactant, a silane coupling agent, an antioxidant, a dissolution accelerator, a filler, and a sensitizer. You may.

(Adhesion aid)
The photosensitive resin composition according to the present embodiment may further contain an adhesion aid. Specifically, a triazole compound or aminosilane can be used as the adhesion aid. Thereby, the affinity between the photosensitive resin composition and the metal member such as Al and Cu can be improved. Therefore, the uniformity of the resin film can be improved.

Specific examples of the triazole compound include 4-amino-1,2,4-triazole, 4H-1,2,4-triazole-3-amine, and 4-amino-3,5-di-2-pyridyl-. 4H-1,2,4-triazole, 3-amino-5-methyl-4H-1,2,4-triazole, 4-methyl-4H-1,2,4-triazole-3-amine, 3,4- Diamino-4H-1,2,4-triazole, 3,5-diamino-4H-1,2,4-triazole, 1,2,4-triazole-3,4,5-triamine, 3-pyridyl-4H- 1,2,4-Triazole, 4H-1,2,4-Triazole-3-carboxamide, 3,5-diamino-4-methyl-1,2,4-triazole, 3-pyridyl-4-methyl-1, Examples thereof include 1,2,4-triazole such as 2,4-triazole and 4-methyl-1,2,4-triazole-3-carboxamide. As the triazole compound, one or a combination of two or more of the above specific examples can be used.

Specific examples of the aminosilane include a condensate of cyclohexene-1,2-dicarboxylic acid anhydride and 3-aminopropyltriethoxysilane, 3,3', 4,4'-benzophenonetetracarboxylic acid dianhydride and 3 -Condensate of aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (amino) Ethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl -3-Aminopropyltrimethoxysilane, N, N'bis [3- (trimethoxysilyl) propyl] ethylenediamine, N, N'-bis- (3-triethoxysilylpropyl) ethylenediamine, N, N'-bis [ 3- (Methyldimethoxysilyl) propyl] ethylenediamine, N, N'-bis [3- (methyldiethoxysilyl) propyl] ethylenediamine, N, N'-bis [3- (dimethylmethoxysilyl) propyl] ethylenediamine, N- [3- (Methyldimethoxysilyl) propyl] -N'-[3- (trimethoxysilyl) propyl] ethylenediamine, N, N'-bis [3- (trimethoxysilyl) propyl] diaminopropane, N, N'- Examples thereof include bis [3- (trimethoxysilyl) propyl] diaminohexane and N, N'-bis [3- (trimethoxysilyl) propyl] diethylenetriamine. As the aminosilane, one or a combination of two or more of the above specific examples can be used.

The lower limit of the content of the adhesion aid in the photosensitive resin composition is, for example, preferably 0.1 part by mass or more, and 1.0 part by mass or more with respect to 100 parts by mass of the alkali-soluble resin. It is more preferably 2.0 parts by mass or more, further preferably 3.0 parts by mass or more.

The upper limit of the content of the adhesion aid in the photosensitive resin composition is, for example, preferably 10 parts by mass or less, and 7 parts by mass or less, based on 100 parts by mass of the alkali-soluble resin. More preferably, it is more preferably 5 parts by mass or less.
When the content of the adhesion aid is within the above numerical range, the adhesion aid is suitably dispersed in the photosensitive resin composition, and the adhesion of the photosensitive resin composition to the adherend can be improved. This is preferable from the viewpoint that foreign matter can be prevented from being mixed between the resin film and the adherend of the resin film and the thickness becomes non-uniform.

(Silane coupling agent)
The photosensitive resin composition according to the present embodiment may further contain a silane coupling agent. Examples of the silane coupling agent include those other than the aminosilane exemplified as the adhesion aid.
Specific examples of the silane coupling agent include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and the like. Epoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; styrylsilanes such as p-styryltrimethoxysilane; 3-methacryloxy Methacrylic silanes such as propylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane; acrylic silanes such as 3-acryloxypropyltrimethoxysilane; Isocyanurate silane; Alkyl silane; Ureid silane such as 3-ureidopropyltrialkoxysilane; Mercaptosilane such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane; ; Titanium-based compounds; Aluminum chelates; Aluminum / silane-based compounds and the like. As the silane coupling agent, one or more of the above specific examples can be blended.

(Thermal crosslinker)
The photosensitive resin composition according to the present embodiment may contain a thermal cross-linking agent that can react with an alkali-soluble resin by heat. As a result, it is possible to improve the mechanical properties such as tensile elongation at break of the cured product obtained by post-baking the photosensitive resin composition. It is also convenient from the viewpoint of improving the sensitivity of the resin film formed by the photosensitive resin composition.
Specific examples of the thermal cross-linking agent include 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol (paraxylene glycol), 1,3,5-benzenetrimethanol, and the like. Methylol groups such as 4,4-biphenyldimethanol, 2,6-pyridinedimethanol, 2,6-bis (hydroxymethyl) -p-cresol, 4,4'-methylenebis (2,6-dialkoxymethylphenol) Phenols such as fluoroglucolside; 1,4-bis (methoxymethyl) benzene, 1,3-bis (methoxymethyl) benzene, 4,4'-bis (methoxymethyl) biphenyl, 3,4'-bis Compounds having an alkoxymethyl group such as (methoxymethyl) biphenyl, 3,3'-bis (methoxymethyl) biphenyl, methyl 2,6-naphthalenedicarboxylate, 4,4'-methylenebis (2,6-dimethoxymethylphenol) Methylol melamine compounds typified by hexamethylol melamine, hexabutanol melamine, etc .; alkoxy melamine compounds such as hexamethoxy melamine; alkoxymethyl glycol uryl compounds such as tetramethoxymethyl glycol uryl; methylol benzoguanamine compounds, methylol ethylene urea, etc. Urea compound; cyano compound such as dicyanoaniline, dicyanophenol, cyanophenylsulfonic acid; isocyanato compound such as 1,4-phenylenediisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate; ethylene Epoxy group-containing compounds such as glycol diglycidyl ether, bisphenol A diglycidyl ether, triglycidyl isocyanurate, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene-based epoxy resin, biphenyl type epoxy resin, phenol novolac resin type epoxy resin. ; Maleimide compounds such as N, N'-1,3-phenylenedimaleimide, N, N'-methylenedimaleimide and the like can be mentioned. As the heat cross-linking agent, one or a combination of two or more of the above specific examples can be used.

The upper limit of the content of the heat-crosslinking agent in the photosensitive resin composition is preferably, for example, 20 parts by mass or less, and more preferably 15 parts by mass or less with respect to 100 parts by mass of the alkali-soluble resin. , 12 parts by mass or less, more preferably 10 parts by mass or less. As a result, even when the heat cross-linking agent has a solvating functional group such as a phenolic hydroxyl group, it is possible to suppress a decrease in chemical resistance after post-baking.

Further, the lower limit of the content of the heat-crosslinking agent in the photosensitive resin composition is preferably, for example, 0.1 part by mass or more, and 1 part by mass or more with respect to 100 parts by mass of the alkali-soluble resin. It is more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, and particularly preferably 8 parts by mass or more.

(Surfactant)
The photosensitive resin composition according to the present embodiment may further contain a surfactant.
The surfactant is not limited, and specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether and polyoxyethylene. Polyoxyethylene aryl ethers such as nonylphenyl ethers; nonionic surfactants such as polyoxyethylene dilaurates and polyoxyethylene dialkyl esters such as polyoxyethylene distearate; Ftop EF301, Ftop EF303, Ftop EF352 (Made by Shin-Akita Kasei Co., Ltd.), Mega Fuck F171, Mega Fuck F172, Mega Fuck F173, Mega Fuck F177, Mega Fuck F444, Mega Fuck F470, Mega Fuck F471, Mega Fuck F475, Mega Fuck F482, Mega Fuck F477 (DIC) , Florard FC-430, Florard FC-431, Novec FC4433, Novec FC4432 (manufactured by 3M Japan), Surfron S-381, Surfron S-382, Surfron S-383, Surfron S-393, Surfron SC-101, Fluorosurfactants commercially available under names such as Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106, (manufactured by AGC Seimi Chemical Co., Ltd.); Organosiloxane co-weight Combined KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.); (meth) acrylic acid-based copolymer Polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like can be mentioned.

Among these, it is preferable to use a fluorine-based surfactant having a perfluoroalkyl group. Examples of the fluorosurfactant having a perfluoroalkyl group include Megafuck F171, Megafuck F173, Megafuck F444, Megafuck F470, Megafuck F471, Megafuck F475, Megafuck F482, and Megafuck. One or more selected from F477 (manufactured by DIC), Surfron S-381, Surfron S-383, Surfron S-393 (manufactured by AGC Seimi Chemical), Novek FC4430 and Novek FC4432 (manufactured by 3M Japan Ltd.) It is preferable to use.

(Antioxidant)
The photosensitive resin composition according to the present embodiment may further contain an antioxidant. As the antioxidant, one or more selected from a phenol-based antioxidant, a phosphorus-based antioxidant and a thioether-based antioxidant can be used. The antioxidant can suppress the oxidation of the resin film formed by the photosensitive resin composition.

Phenol-based antioxidants include pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3). -T-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} 2,4,8,10-tetraoxaspiro [5,5] undecane,
Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ], 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-t-butyl-4-hydroxyphenyl) propionate, distearyl ( 3,5-di-t-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycolbis [(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-t) -Butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-t-butyl-4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6) -T-butyl-6-butylphenol), 2,-2'-methylenebis (4-ethyl-6-t-butylphenol), bis [3,3-bis (4-hydroxy-3-t-butylphenyl) butyl Acid] Glycol ester, 4,4'-butylidenebis (6-t-butyl-m-cresol), 2,2'-etylidenebis (4,6-di-t-butylphenol), 2,2'-etylidenebis (2,2'-etyldenbis (4,6-di-t-butylphenol) 4-s-Butyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, bis [2-t-butyl-4-methyl- 6- (2-Hydroxy-3-t-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, 1,3,5-Tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-Tris [(3,5-di-t-) Butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 2-t-butyl-4-methyl- 6- (2-acryloyloxy-3-t-butyl-5-methylbenzyl) phenol, 3,9-bis ( 1,1-dimethyl-2-hydroxyethyl) -2,4-8,10-tetraoxaspiro [5,5] undecane-bis [β- (3-t-butyl-4-hydroxy-5-methylphenyl) Propionate], Triethyleneglycolbis [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 1,1'-bis (4-hydroxyphenyl) cyclohexane, 2,2'-methylenebis (4-Methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis (6- (1-methylcyclohexyl) -4-methylphenol) ), 4,4'-Butylidenebis (3-methyl-6-t-butylphenol), 3,9-bis (2- (3-t-butyl-4-hydroxy-5-methylphenylpropionyloxy) 1,1- Dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-bis (3,5) -Di-t-butyl-4-hydroxybenzyl) sulphide, 4,4'-thiobis (6-t-butyl-2-methylphenol), 2,5-di-t-butylhydroquinone, 2,5-di- t-amylhydroquinone, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2,4-dimethyl-6- (1-methylcyclohexyl,) Examples include styrenated phenol, 2,4-bis ((octylthio) methyl) -5-methylphenol, and the like.

Phosphorus antioxidants include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2,4-di-t-butylphenylphosphite), and tetrakis (2). , 4-di-t-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis- (2,6) -Dicumylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, tris (mixed monoand di-nonylphenylphosphite), bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methoxycarbonylethyl-phenyl) pentaerythritol diphosphite, bis (2,6-di-t) -Butyl-4-octadecyloxycarbonylethylphenyl) pentaerythritol diphosphite and the like.

Thioether-based antioxidants include dilauryl-3,3'-thiodipropionate and bis (2-methyl-4- (3-n-dodecyl) thiopropionyloxy) -5-t-butylphenyl) sulfide. , Distearyl-3,3'-thiodipropionate, pentaerythritol-tetrakis (3-lauryl) thiopropionate and the like.

(Filler)
The photosensitive resin composition according to the present embodiment may further contain a filler. As the filler, an appropriate filler can be selected according to the mechanical properties and thermal properties required for the resin film made of the photosensitive resin composition.

Specific examples of the filler include an inorganic filler and an organic filler.
Specific examples of the inorganic filler include fused crushed silica, fused spherical silica, crystalline silica, secondary aggregated silica, and fine powder silica; alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, and silicon carbide. , Metal compounds such as aluminum hydroxide, magnesium hydroxide, titanium white; talc; clay; mica; glass fiber and the like. As the inorganic filler, one or a combination of two or more of the above specific examples can be used.

Specific examples of the organic filler include organosilicone powder and polyethylene powder. As the organic filler, one or a combination of two or more of the above specific examples can be used.

(Preparation of photosensitive resin composition)
The method for preparing the photosensitive resin composition in the present embodiment is not limited, and a known method can be used depending on the components contained in the photosensitive resin composition.
For example, each of the above components can be prepared by mixing and dissolving in a solvent. This makes it possible to obtain a photosensitive resin composition as a varnish.

In the present embodiment, from the viewpoint that the contact angle with respect to various materials existing on the substrate of the panel level package is within a desired value, all the steps for adjusting the photosensitive resin composition may be performed in a nitrogen atmosphere. preferable. As a result, the components in the photosensitive resin composition that are active against the components contained in air such as oxygen are inactivated. Therefore, the dispersibility of the alkali-soluble resin in the photosensitive resin composition can be improved.

(Use)
The photosensitive resin composition of the present embodiment is used for forming a resin film such as a permanent film or a resist film for a panel level package. Among these, for example, it is preferable to use it for applications using a permanent film.
In the present embodiment, the resin film is a dry film or a cured film of the photosensitive resin composition. That is, the resin film according to the present embodiment is formed by drying or curing the photosensitive resin composition.

The permanent film is, for example, a resin film obtained by applying a photosensitive resin composition, then prebaking, exposing and developing, patterning into a desired shape, and curing by post-baking. It is composed. The permanent film can be used as a protective film, an interlayer film, a dam material, or the like of an electronic device.

The resist film is composed of, for example, a resin film obtained by applying a photosensitive resin composition to an object to be masked by the resist film and removing a solvent from the photosensitive resin composition.

In the process of manufacturing the permanent film or the resist film, the step of applying the photosensitive resin composition is preferably performed by, for example, a slit coat. As a result, a uniform resin film can be formed on the entire surface of the panel.

The thickness of the permanent film or the resist film is not particularly limited, but is, for example, about 2 to 30 μm, preferably about 5 to 20 μm.
Various methods can be applied to remove the solvent after coating the photosensitive resin composition (for example, heating), but considering that the panel level package has a relatively large area, it is dried under reduced pressure. It is preferable to apply. That is, it is preferable to dry the panel coated with the photosensitive resin composition in a reduced pressure environment (for example, in an environment of 30 Pa or less). It should be noted that vacuum drying has the advantage of reducing microbubbles that may occur during coating.

When prebaking is performed, the conditions are, for example, about 5 seconds to 30 minutes at 70 to 160 ° C.
For exposure, electromagnetic waves of various wavelengths, particle beams and the like can be used. For example, ultraviolet rays such as g-rays and i-rays, visible rays, lasers, X-rays, electron beams and the like are used. It is preferably ultraviolet light such as g-ray or i-line. The exposure amount is appropriately set according to the sensitivity of the photosensitive adhesive composition and the like, but is, for example, about 30 to 3000 mJ / cm ² . The exposure is usually performed by using an appropriate mask pattern or the like.
For development, various developers can be applied. For example, alkali metal carbonates, alkali metal hydroxides, alkaline developers such as tetramethylammonium hydroxide, dimethylformamide, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, acetic acid. Examples thereof include an organic developer such as butyl. Among these, an alkaline developer is preferable, and an aqueous solution of tetramethylammonium hydroxide is particularly preferable. Examples of the method for supplying the developing solution include spraying, paddle, and dipping. The spray method is preferable in terms of processing a large-area panel.
The post-baking conditions (curing conditions) are not particularly limited, but are, for example, 30 to 300 minutes at 80 to 300 ° C.

An electronic device including a resin film obtained by curing the photosensitive resin composition of the present embodiment, specifically, a panel level package will be described.
Panel-level packages have various structures such as cores, chips, and prepregs (reinforced plastic materials in which fibrous reinforcing materials such as glass cloth and carbon fiber are evenly impregnated with thermosetting resins such as epoxy). It is sealed or fixed with a sheet-shaped encapsulant to form a panel. In addition, metals such as Cu and Al are usually used for the panel level package as wiring (these metals are usually incorporated into the panel level package by a plating method or a sputtering method), and a passivation film such as silicon nitride is also used. Can be included. Further, in the panel level package, as one aspect, a resin film obtained by curing the photosensitive resin composition (for example, a resin film obtained by curing the photosensitive resin composition of the present embodiment) is formed on the surface thereof. ..

That is, on the surface of the panel level package, prepreg, Cu foil for forming a conductor circuit pattern, Cu / Al (wiring, pad, etc.) formed by sputtering, a cured product of a photosensitive resin composition, and silicon nitride passivation. The film, Si chip, cured product of the encapsulant, etc. can be exposed.
As described above, the photosensitive resin composition of the present embodiment forms a uniform film in various panel-level packages as described above because θ _max −θ _min and θ _ave are appropriate numerical values. It is also possible to suppress sagging at the edge portion.

The shape and size of the panel level package is, for example, a substantially rectangular shape having a length of 300 to 800 mm and a width of 300 to 800 mm. The industry has proposed, for example, 470 mm x 370 mm, 610 mm x 457 mm (24 inches x 18 inches), and panel level packages. By collectively manufacturing such a large-area package, it is possible to reduce the cost of manufacturing the electronic device.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the description of these examples.

First, the raw materials used in Examples and Comparative Examples will be described in detail.

<Alkali-soluble resin>
An alkali-soluble resin 1 which is a polyamide resin was prepared by the following procedure.
Diphenyl ether-4,4'-dicarboxylic acid 206.58 g represented by the following formula (DC2) in a four-port glass separable flask equipped with a thermometer, a stirrer, a raw material input port and a dry nitrogen gas introduction tube. 170.20 g (0) of a mixture of dicarboxylic acid derivatives obtained by reacting (0.800 mol) with 216.19 g (1.600 mol) of 1-hydroxy-1,2,3-benzotriazole / monohydrate. .346 mol), 4.01 g (0.047 mol) of 5-aminotetrazole, and 45.22 g (0.196 mol) of 4,4'-methylenebis (2-aminophenol) represented by the following formula (DA2). 56.24 g (0.196 mol) of 4,4'-methylenebis (2-amino-3,6 dimethylphenol) represented by the following formula (DA3) was added. Then, 578.3 g of N-methyl-2-pyrrolidone was added into the separable flask to dissolve each raw material component. Next, the reaction was carried out at 90 ° C. for 5 hours using an oil bath. Next, 24.34 g (0.141 mol) of 4-ethynylphthalic anhydride and 121.7 g of N-methyl-2-pyrrolidone were added to the separable flask, and the reaction was carried out at 90 ° C. for 2 hours with stirring. After that, the reaction was terminated by cooling to 23 ° C.

The filtrate obtained by filtering the reaction mixture in the separable flask was put into a solution of water / isopropanol = 7/4 (volume ratio). Then, the precipitate was separated by filtration, washed thoroughly with water, and then dispersed in NMP (N-methylpyrrolidone) without drying to obtain a solution of the target alkali-soluble resin 1. The weight average molecular weight Mw of the obtained alkali-soluble resin 1 was 18081.

<Photosensitizer>
The photosensitizer used in each Example and each Comparative Example will be described in detail.

(Photosensitive agent 1)
The photosensitive agent 1 which is a diazoquinone compound was synthesized by the following procedure.
11.04 g (0.026 mol) of the compound represented by the following formula (P-1) and 1, 18.81 g (0.070 mol) of 2-naphthoquinone-2-diazide-5-sulfonyl chloride and 170 g of acetone were added and stirred to dissolve them.

Then, while cooling the flask in a water bath so that the temperature of the reaction solution did not exceed 35 ° C., a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise. After reacting as it was at room temperature for 3 hours, 1.05 g (0.017 mol) of acetic acid was added, and the reaction was further carried out for 30 minutes. Then, after filtering the reaction mixture, the filtrate was put into a mixed solution of water / acetic acid (990 mL / 10 mL). The precipitate was then collected by filtration, washed thoroughly with water and then dried under vacuum. As a result, the photosensitive agent 1 represented by the structure of the following formula (Q-1) was obtained.

<Adhesion aid>
-Adhesion aid 1: Silane coupling agent represented by the following formula (9) -Adhesion aid 2: N, N'-bis [3- (trimethoxysilyl) propyl] represented by the following formula (S1) Ethylenediamine (manufactured by Shin-Etsu Chemical Co., Ltd., X-12-5263HP)

The adhesion aid 1 is synthesized as follows.
Cyclohexene-1,2-dicarboxylic acid anhydride (45.6 g, 300 mmol) was dissolved in N-methyl-2-pyrrolidone (970 g) in an appropriately sized reaction vessel equipped with a stirrer and a condenser and kept at constant temperature. The temperature was adjusted to 30 ° C. in the tank. Then, 3-aminopropyltriethoxysilane (62 g, 280 mmol) was charged into the dropping funnel, and the solution was added dropwise over 60 minutes. After the dropping was completed, the mixture was stirred under the conditions of 30 ° C. and 18 hours to obtain a silane coupling agent represented by the above formula (9).

<Thermal crosslinker>
・ Thermal cross-linking agent 1: Fluorogluside ・ Thermal cross-linking agent 2: Paraxylene glycol (manufactured by Ihara Nikkei, PXG)

<Surfactant>
-Surfactant 1: Fluorine-based surfactant (manufactured by 3M Japan Ltd., FC4430)
-Surfactant 2: Liquid silicone compound having a polyether group (manufactured by Big Chemie Japan, BYK-333)

<Solvent>
The following solvents 1 to 4 were used as the solvent.
-Solvent 1: N-methylpyrrolidone (NMP)
-Solvent 2: γ-Butyrolactone (GBL)
Solvent 3: 2-methoxy-1-methyl ethyl acetate (PGMEA)
-Solvent 4: Tetramethylurea (TMU)

(Preparation of photosensitive resin composition)
The photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were prepared as follows.
First, the solvents were mixed according to the blending ratios shown in Table 1 below to prepare a mixed solvent.
Next, each raw material component other than the solvent is added to the mixed solvent, stirred, and filtered through a PTFE membrane filter having a pore size of 0.2 μm, whereby the varnish of the photosensitive resin composition of each Example and each Comparative Example is used. Got The amount of the mixed solvent was adjusted so that the solid content concentration was 10 to 40% by mass and the viscosity was about 50 to 2000 mPa · s in each composition.
The amount of the surfactant added is the concentration (ppm) of the photosensitive resin composition containing the mixed solvent with respect to the entire varnish.

In the step of producing the varnish of the photosensitive resin composition of each example, the above-mentioned alkali-soluble resin is dissolved in a mixed solvent while being dissolved in NMP (N-methylpyrrolidone), and the solvent is completely removed from the alkali-soluble resin. Did not include the process of volatilization.
In addition, the steps for preparing the varnish of the photosensitive resin composition of each example were all carried out in a nitrogen atmosphere from the preparation of the mixed solvent. On the other hand, the compositions of each Comparative Example were prepared under a normal Air atmosphere.

(Contact angle)
For the photosensitive resin compositions of each Example and Comparative Example, plated copper (CCL) whose surface was washed with a 5 wt% sulfuric acid aqueous solution, a substrate having a sputtered Cu as a surface layer, a substrate having a sputtered Al as a surface layer, and a CVD film of silicon nitride. The contact angle with respect to the substrate composed of the substrate having the surface layer, the bare silicon wafer, and the cured film (PSPI) of the photosensitive resin composition was measured.

As the CCL, the one prepared by the following procedure was used.
(1) An insulating sheet with a base material was prepared according to the description in paragraphs 0066 and 0067 of International Publication No. 2008/044552.
(2) A multilayer substrate material R-1766 (Panasonic, 0.4 mm thick) is prepared and laminated on the front and back of the multilayer substrate material with the insulating sheet surface of the insulating sheet with a base material produced in (1) above facing inside. rice field. This was vacuum-heated and pressure-molded at a temperature of 100 ° C. and a pressure of 1 MPa using a vacuum-pressurized laminator device, and then heat-cured at 170 ° C. for 60 minutes with a hot-air drying device. As a result, a multi-layer structure was obtained.
(3) The substrate is peeled off from the multilayer structure obtained in (2) above, immersed in a swelling solution at 70 ° C (Atotech Japan, "Swelling Dip Securigant P") for 10 minutes, and further immersed at 80 ° C. Was immersed in an aqueous solution of potassium permanganate (Atotech Japan, "Concentrate Compact CP") for 20 minutes. Then, it was neutralized and roughened.
After undergoing the steps of degreasing, catalyst application, and activation, an electroless copper-plated film having a thickness of about 1 μm and an electroplated copper having a thickness of 30 μm was formed, and annealed at 200 ° C. for 60 minutes with a hot air drying device. rice field.
(4) The substrate with plated copper obtained in (3) above was immersed and washed with a 5 wt% sulfuric acid aqueous solution for 30 seconds, then washed with pure water, and air-dried with _N2 gas.
From the above, a substrate having plated copper on the surface was obtained.

As the CVD film for spattered Cu, spattered Al, and silicon nitride, those purchased from Kyodo International Co., Ltd. were used.
As the bare silicon wafer, the one purchased from Advantec Co., Ltd. was used.
For PSPI, a substrate having a film thickness of 10 μm as a surface layer obtained by applying the photosensitive resin composition of each example or comparative example on a silicon wafer and curing at 220 ° C. for 60 minutes was used.

As a specific procedure for measuring the contact angle, first, for each of the compositions of Examples and Comparative Examples, the viscosity measured by an E-type viscometer at a rotation frequency of 100 rpm, a temperature of 25 ° C., and after rotation for 300 seconds is 50 mPa · s. The viscosity was adjusted with γ-butyrolactone.
Then, at a temperature of 25 ° C., the contact angle 10 seconds after the varnish of the photosensitive resin composition whose viscosity was adjusted above was dropped on each substrate was evaluated by the sessile drop method. The measurement was performed using a contact angle meter (DROPMASTER-501, manufactured by Kyowa Interface Science Co., Ltd.).
As a result, the contact angles (θ _CCL , θ _Cu , θ _Al , θ _SiN , θ _Si , θ _PSPI ) with respect to CCL, spatter Cu, spatter Al, silicon nitride, bare silicon wafers, and PSPI were evaluated. Further, the average values of the obtained θ _CCL , θ _Cu , θ _Al , θ _SiN , and θ _Si were calculated as θ _ave , the standard deviation was set to θ _st , the maximum value was set to θ _max , and the minimum value was set to θ _min . The evaluation results are shown in Table 1 below. The unit is "°".

(Evaluation of coatability (uniformity of film thickness and sagging of edges))
When the photosensitive resin compositions of each Example and Comparative Example were used as a permanent film for a panel level package, the uniformity of the film thickness of the permanent film and the coatability such as sagging (deficiency) of the edge portion of the permanent film were obtained. Evaluation was performed. Details will be described below.

First, a copper-clad laminate having a copper circuit, a chip made of silicon nitride having a pad made of aluminum, and a substrate having a chip made of silicon (Si) having a pad made of aluminum were prepared.
The photosensitive resin compositions of each Example and each Comparative Example were coated on the surface of this substrate by a slit coating method, and dried under reduced pressure. In this evaluation, as the photosensitive resin composition, the viscosity of γ-butyrolactone was 50 mPa. The one adjusted to s was applied.

Then, using a hot plate, it was prebaked at a temperature of 110 ° C. for 4 minutes. As a result, a prebaked photosensitive resin composition having a film thickness of 10.9 μm was obtained.
The prebaked photosensitive resin composition was pattern-masked and subjected to broadband exposure using a broadband mask aligner (MA8 manufactured by SUS MicroTech). After the exposure, a development process was carried out using a 2.38 mass% tetramethylammonium aqueous solution as a developer to remove pattern masking. For pattern masking, a mask (Mask manufactured by Toppan Printing Co., Ltd., test chart No. 1) on which a remaining pattern having a width of 0.88 μm to 50 μm and a punching pattern were drawn was used. Then, using an oven, a photosensitive resin composition was obtained by post-baking at a temperature of 220 ° C. for 1 hour under a nitrogen atmosphere.

The thickness uniformity of the obtained post-baked photosensitive resin composition was evaluated. Specifically, the thickness of any three points of the remaining pattern part is measured, and the difference in thickness between the part with the largest thickness and the part with the smallest thickness is 2 μm or less, which can be said to be a practically acceptable level. Those exceeding 2 μm were designated as “○”, and those exceeding 2 μm were designated as “×”.

In addition, the obtained post-baked photosensitive resin composition was observed, and the presence or absence of sagging of the edge portion of the permanent film (corresponding to the end portion when the film was formed by the slit coat) was determined by the following criteria according to the following criteria. evaluated.
◯: No sagging was observed.
X: Sauce was observed.

As shown in Table 1 above, in the photosensitive resin composition of each example, the uniformity of the coating film when forming the resin film is improved in the step of preparing the panel level package, and sagging occurs at the edge portion. It was confirmed that it was possible to suppress this.
On the other hand, the photosensitive resin composition of each comparative example (θ _ave is more than 30 ° and θ _max −θ _min is 40 ° or more) is inferior to the examples in terms of the uniformity of the coating film and the sagging of the edge portion. It was performance.

Claims (10)

A photosensitive resin composition used to form a permanent film or a resist film for a panel level package.
Contains an alkali-soluble resin, a photosensitive agent, and a solvent,
The difference θ _max −θ _min between the maximum value θ _max of the contact angle and the minimum value θ _min of the contact angle measured according to the following measurement condition 1 is 40 ° or less.
A photosensitive resin composition having an average value θ _ave of contact angles of the photosensitive resin composition measured according to the following measurement condition 1 of 10 to 30 °.
(Measurement condition 1)
The photosensitive resin composition was viscous-adjusted with γ-butyrolactone by an E-type viscometer at a rotation frequency of 100 rpm, a temperature of 25 ° C, and a viscosity measured after rotation for 300 seconds at 50 mPa · s, and the temperature was 25 ° C. Then, 2 μL is dropped on each of the following substrates. Regarding the contact angles θ _CCL , θ _Cu , θ _Al , θ _SiN and θ _Si measured for each substrate 10 seconds after dropping, the maximum is θ _max , the minimum is θ _min , and the average value is θ _ave . do.
(substrate)
As the substrate, plated copper whose surface is washed with a 5 wt% sulfuric acid aqueous solution, a substrate whose surface layer is sputtered Cu, a substrate whose surface layer is sputtered Al, a substrate whose surface layer is a silicon nitride CVD film, and a bare silicon wafer are used. The correspondence between the substrate and the contact angle is as follows.
-The contact angle when using plated copper whose surface has been washed with a 5 wt% sulfuric acid aqueous solution is defined as θ _CCL .
-The contact angle when a substrate having spattered Cu as the surface layer is used as the substrate is set to θ _Cu .
-The contact angle when a substrate having spatter Al as the surface layer is used as the substrate is θ _Al .
-The contact angle when a substrate having a silicon nitride CVD film as a surface layer is used as the substrate is set to θ _SiN .
-The contact angle when a bare silicon wafer is used as the substrate is θ _Si . The photosensitive resin composition according to claim 1.
A photosensitive resin composition having a standard deviation θ _st of θ _CCL , θ _Cu , θ _Al , θ _SiN and θ _Si of 25 ° or less. The photosensitive resin composition according to claim 1 or 2.
A photosensitive resin composition having a θ _max of 25 to 50 °. The photosensitive resin composition according to any one of claims 1 to 3.
A photosensitive resin composition having a θ _min of 3 to 15 °. The photosensitive resin composition according to any one of claims 1 to 4.
With respect to a substrate having a film having a film thickness of 10 μm formed of the photosensitive resin composition as a surface layer, when the contact angle measured according to the measurement condition 1 is θ _PSPI , the θ _PSPI is 10 to 30 °. Resin composition. The photosensitive resin composition according to any one of claims 1 to 5.
The alkali-soluble resin is one or more selected from the group consisting of polyamide resins, polybenzoxazole resins, polyimide resins, phenol resins, hydroxystyrene resins and cyclic olefin resins. The photosensitive resin composition according to any one of claims 1 to 6.
The photosensitive agent is a photosensitive resin composition which is a diazoquinone compound. The photosensitive resin composition according to any one of claims 1 to 7.
The photosensitive resin composition is used to form the permanent film for a panel level package.
The permanent film is a photosensitive resin composition used as an interlayer insulating film, a surface protective film or a dam material. A resin film obtained by curing the photosensitive resin composition according to any one of claims 1 to 8. An electronic device comprising the resin film according to claim 9.