JP7363030B2 - Resin composition, cured film, method for producing relief pattern of cured film, electronic component, semiconductor device, method for producing electronic component, method for producing semiconductor device - Google Patents

Description

The present invention relates to a resin composition. More specifically, the present invention relates to a resin composition suitable for use in surface protective films of semiconductor devices, interlayer insulating films, insulating layers of organic electroluminescent devices, and the like.

Conventionally, polyimide resins, polybenzoxazole resins, and the like, which have excellent heat resistance and mechanical properties, have been widely used for surface protection films, interlayer insulating films, etc. of semiconductor elements of electronic devices. When polyimide or polybenzoxazole is used as a surface protection film or an interlayer insulating film, one method for forming through holes and the like is etching using a positive photoresist. However, this method requires the steps of applying and peeling off the photoresist, and has the problem of being complicated. Therefore, studies have been conducted on heat-resistant materials that have been imparted with photosensitivity for the purpose of streamlining the work process.

Usually, polyimide and polybenzoxazole are obtained by thermally dehydrating and ring-closing the coating film of their precursor to obtain a thin film having excellent heat resistance and mechanical properties. In that case, high-temperature firing usually around 350°C is required. However, for example, MRAM (Magnetoresistive Random Access Memory), which is a promising next-generation memory, and sealing resin are sensitive to high temperatures. Therefore, in order to be used as a surface protection film for such elements or an interlayer insulation film for fan-out wafer level packages that form rewiring structures on the sealing resin, it is cured by baking at a low temperature of about 250°C or less. There is a need for polyimide resins or polybenzoxazole resins that can provide highly reliable film properties comparable to those obtained by baking conventional materials at high temperatures of around 350°C.

Further, in recent years, semiconductor packages have become increasingly finer in wiring due to demands for higher integration, smaller size, and higher speed. Along with this, there has been a demand for photosensitive resin compositions that can form fine patterns even in surface protective films, interlayer insulating films, and the like.

On the other hand, when the heat-resistant resin composition is used for applications such as semiconductors, the film after heat curing remains as a permanent film within the device. For this reason, the physical properties of the film after heating and curing are important, and after confirming that the physical properties of the cured film meet the required specifications, especially the elongation, after reliability evaluation, which is an accelerated test in actual use, the semiconductor package is manufactured. Served. Furthermore, for reliability in a semiconductor package, adhesion to a material formed on the surface of a semiconductor chip is important. In particular, when used as an insulating film between wiring layers of a wafer level package, adhesion to metal materials used for electrodes, wiring, etc. is important. However, resin compositions containing the above-mentioned low-temperature curable resins have a problem in that they have low adhesion to metals used as wiring materials. In particular, in the case of cured resin films made from photosensitive resin compositions that can form patterns, additives such as photosensitizers, sensitizers, acid generators, and solubility regulators that make up the composition remain hard even after heat curing. Because it remained in the film, the adhesion strength and physical properties were lower than those without additives.

To address these issues, we have developed a photosensitive resin composition that suppresses copper corrosion by adding a copper discoloration inhibitor to the photosensitive resin (see Patent Document 1), and a heterocyclic compound in polybenzoxazole having an aliphatic group. A photosensitive resin composition (see Patent Document 2) has been disclosed in which adhesion to copper and high elongation can be obtained by adding .

In addition to photosensitive resin compositions, we are also considering processing already closed ring polyimides using aliphatic groups without using photosensitizers using carbon dioxide laser (see Patent Document 3), and using fluororesin and other resins for circuit board applications. An example of a cured film obtained by ablating a film obtained by mixing has been reported (see Patent Document 4).

Japanese Patent Application Publication No. 2011-169980 Japanese Patent Application Publication No. 2010-96927 International Publication No. 2010/143667 Japanese Patent Application Publication No. 7-235743

However, cured films of photosensitive resin compositions in which a copper discoloration inhibitor is added to a photosensitive resin, or photosensitive resin compositions in which a heterocyclic compound is added to polybenzoxazole having an aliphatic group, cannot be cured by high-temperature holding tests or constant temperature tests. The elongation and strength after reliability evaluations such as high-humidity tests and thermal cycle tests were low, and when a multilayer structure was formed, there were problems with cracks occurring in the cured film and peeling from metal wiring. In addition, closed ring polyimide using aliphatic groups has problems such as the heat generated by laser processing leaving residue on the pattern and abnormal shapes, and low strength, such as insulating films between wiring layers of wafer level packages. When used for this purpose, there was a problem of cracks occurring after reliability evaluation. In addition, films containing fluororesin have low elongation and strength, so cracks occur in semiconductor packages where fine wiring is formed, and since fluororesin does not absorb ultraviolet rays, it also leaves residue during ablation processing. There was a problem in that it was difficult to form fine patterns without blemishes.

The present invention has been made in view of the problems associated with the conventional technology as described above, and it is possible to obtain a cured film that can be cured at a low temperature of 200°C or less and can be formed into a fine pattern using a UV laser. Provided is a resin composition for ablation processing that allows highly reliable electronic components and semiconductor devices to be obtained.

In order to solve the above problems, the present invention is characterized by the following configurations.
[1] A resin composition containing (a) a resin, (b) a solvent,
A resin composition for ablation processing using a UV laser, wherein the resin (a) is a resin having a polyimide precursor structure with an imidization rate of 5% or more and less than 90%.
[2] The resin composition according to [1], wherein a cured film obtained by curing the resin composition has a tensile elongation of 50% or more and a tensile strength of 150 to 450 MPa.
[3] The resin composition according to [1] or [2], further containing (c) a basic additive.
[4] The resin composition according to any one of [1] to [3], wherein the resin (a) contains a carboxylic acid residue, and the esterification rate of the carboxylic acid residue is 10% or more and less than 90%. .
[5] The resin composition according to [4], wherein the esterified substituent of the carboxylic acid residue in the resin (a) is an alkyl group or an alkyl ether group having a molecular weight of 100 or less.
[6] Diamine residues and carboxylic acid residues containing the structure represented by general formula (1), assuming that the total of all carboxylic acid residues and all amine residues contained in the resin (a) is 100 mol%. The resin composition according to any one of [1] to [5], wherein the proportion of acid residues in total is 10 to 99 mol%.

(In the general formula (1), R represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. a and b are integers of 0 to 4. * mark represents a bonding part.)
[7] The resin (a) has an alicyclic diamine residue and a carboxylic acid residue structure in which two or more benzene rings are bonded by a single bond,
The alicyclic diamine residue has one or more structures selected from the group consisting of general formula (2), general formula (3), and general formula (4), [1] to [6] The resin composition according to any one of the above.

(In general formula (2), the * mark represents a bonding part.)

(In general formula (3), R ¹ and R ² may be the same or different, and each represents a hydrogen atom, a methyl group, or a trifluoromethyl group. In addition, m represents an integer within the range of 1 to 10. (In addition, the asterisk (*) represents the joint.)

(In general formula (4), R ³ and R ⁴ may be the same or different, and each represents a hydrogen atom, a methyl group, or a trifluoromethyl group. Also, the mark * represents a bonding part.)
[8] The basic additive (c) is an additive having a pH of 9.5 to 11.5, and the content of the basic additive (c) is 0.1 part by mass with respect to 100 parts by mass of the (a) resin. -10 parts by mass of the resin composition according to any one of [3] to [7].
[9] The resin composition according to any one of [3] to [8], wherein the basic additive (c) is an imidazole derivative having two or more substituents.
[10] The resin composition according to any one of [1] to [9], wherein the resin (a) is a resin having a polyimide precursor structure with an imidization rate of 20% or more and less than 70%.
[11] The resin composition according to any one of [1] to [10], further comprising (d) a crosslinking agent, wherein the (d) crosslinking agent has three or more methylol groups or alkoxymethyl groups.
[12] The resin composition according to any one of [1] to [11], further comprising (e) a surfactant, wherein the (e) surfactant is an acrylic polymer.
[13] A cured film obtained by curing the resin composition according to [1] to [12] and ablated with a UV laser.
[14] The cured film according to [13], wherein the UV laser is an excimer laser.
[15] The cured film according to [14], wherein the UV laser is a KrF excimer laser.
[16] A cured film comprising a step of applying the resin composition according to any one of [1] to [12] onto a substrate, a step of heat treatment at 180° C. or less, and a step of ablation processing with a UV laser. A method for manufacturing relief patterns.
[17] An electronic component or semiconductor device, in which the cured film according to any one of [13] to [15] is disposed as an interlayer insulating film between rewirings.
[18] The electronic component or semiconductor device according to [17], wherein the rewiring is a copper metal wiring, and the width of the copper metal wiring and the interval between adjacent wirings are 5 μm or less.
[19] The cured film according to any one of [13] to [15] is disposed as an interlayer insulating film between rewirings on a sealing resin substrate on which a silicon chip is disposed, [17] or [ 18]. The electronic component or semiconductor device according to [18].
[20] The semiconductor electronic component or semiconductor device according to [17] to [19], in which the width of the metal wiring and the interval between adjacent wirings become narrower as the rewiring layer according to [17] approaches the semiconductor chip.
[21] A step of disposing the cured film according to any one of [13] to [15] as an interlayer insulating film between rewirings on the support substrate on which the temporary pasting material is disposed;
A step of placing a silicon chip and a sealing resin thereon;
After that, it includes a step of peeling off the support substrate on which the temporary pasting material is placed and the rewiring.
A method for manufacturing electronic components or semiconductor devices.

Provides a resin composition for ablation processing that can be cured at a low temperature of 200°C or less and that can be used to form a fine pattern using a UV laser, resulting in highly reliable electronic components and semiconductor devices. do.

FIG. 2 is a diagram showing an enlarged cross section of a pad portion of a semiconductor device having bumps. FIG. 3 is a diagram showing a detailed method for manufacturing a semiconductor device having bumps. FIG. 1 is an enlarged cross-sectional view of a pad portion of a semiconductor device showing an embodiment of the present invention. 1 is a sectional view of a coil component of an inductor device showing an embodiment of the present invention. FIG. 2 is a diagram showing a method for manufacturing a semiconductor device using RDL first. FIG. 2 is a cross-sectional view of an example of a TFT substrate.

The resin composition of the present invention is a resin composition containing (a) a resin, (b) a solvent, and
A resin composition for ablation processing using a UV laser, wherein the resin (a) is a resin having a polyimide precursor structure with an imidization rate of 5% or more and less than 90%.

The polyimide precursor structure in the resin (a) is characterized in that the imidization rate is 5% or more and less than 90%. When the imidization rate is 5% or more, the amount of carboxylic acid in the polyimide precursor decreases, and metal diffusion that occurs due to interaction between the carboxylic acid in the polyimide precursor and metal wiring during thermal curing is suppressed. . Therefore, the cured film has a low content of metal components, and a fine pattern (high resolution) without residue can be obtained by ablation processing using a UV laser. Furthermore, since metal corrosion is suppressed, adhesion can be improved. Furthermore, it is possible to suppress the deterioration in film properties that occurs when the polyimide precursor cleaves during heat curing, resulting in film properties suitable for ablation processing using a UV laser and a highly reliable cured film. Therefore, it is preferable.

In addition, when the imidization rate is less than 90%, it is possible to suppress partial aggregation of the polymer due to imide groups in the coating film, so it is possible to form a fine pattern without residue when ablating the cured film using a UV laser. This method is preferable because a cured film with high resolution and high reliability can be obtained.

In view of the balance between film properties, metal adhesion, and ablation processability, the imidization rate of the polyimide precursor structure is preferably 20% or more, more preferably 30% or more. Further, it is preferably less than 70%, and more preferably less than 50%.

It is preferable that the cured film obtained by curing the resin composition of the present invention has a tensile elongation of 50% or more and a tensile strength of 150 to 450 MPa.

When the elongation is 50% or more and the strength is 150 MPa or more, the decomposition and deterioration of the cured film at the pattern processing interface can be suppressed during UV laser irradiation, and the elongation is 50% or more and the tensile strength is 450 MPa or less. In this case, pattern processing is possible even if the energy irradiation time is short, so fine patterns can be formed without causing abnormalities in shape. Therefore, a high-resolution pattern that can withstand reliability evaluation can be obtained.

In the present invention, the polyimide precursor means a resin structure having a structure represented by general formula (5).

(In the general formula (5), R ⁵ represents a trivalent to hexavalent organic group, R ⁶ represents a divalent organic group, R represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and m represents (It is an integer from 1 to 4, and n is an integer from 10 to 100,000.)
In general formula (5), R ⁵ and R ⁶ may have a phenolic hydroxyl group or an aliphatic chain to improve crosslinkability and adhesion, but pattern abnormalities and residues after ablation processing may be suppressed. Therefore, an aromatic group without a phenolic hydroxyl group is preferable. Moreover, it is preferable that it does not contain fluorine. Fluorine does not absorb in the ultraviolet region, so even if it contains resin or additives that absorb in the ultraviolet region, it cannot be removed and a residue is generated when forming fine patterns during ablation processing. However, since interaction with molecular chains and metals is suppressed, physical properties and adhesion are reduced, so it is preferable not to contain fluorine.

In the above general formula (5), R ⁵ represents an acid dianhydride or a residue of trimellitic acid, and is a trivalent to hexavalent organic group.

Specifically, the acid dianhydride includes pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 2,3,3',4'-biphenyltetracarboxylic acid. Dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'- Benzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1- Bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis (2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5, 6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene Acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride Anhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, 5-( 2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic dianhydride, bicyclo[2. 2.2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3,5,6-tricarboxy- 2-Norbornane acetic dianhydride, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3- Diones and acid dianhydrides with the structure shown in the formula below, compounds in which some of the hydrogen atoms of these aromatic rings and hydrocarbons are substituted with alkyl groups having 1 to 10 carbon atoms, tricarboxylic acid monoanhydrides, etc. Examples include trimellitic anhydride (1,2,4-tricarboxybenzene-1,2 anhydride), hemimellitic anhydride (1,2,3-tricarboxybenzene-1,2 anhydride), 2, 3,5-Tricarboxynaphthalene-2,3-anhydride, 4-(4-carboxyphenoxy)phthalic anhydride, 1,2,4-carboxycyclohexane-1,2-anhydride, 1,2,3-trianhydride Examples include, but are not limited to, carboxycyclopropane-1,2 anhydride, 1,2,3-tricarboxycyclobutane-1,2 anhydride, aconitic acid anhydride, and the like. These can be used alone or in combination of two or more

R ¹⁶ represents an oxygen atom, C(CH ₃ ) ₂ or SO ₂ , and R ¹⁷ and R ¹⁸ represent a hydrogen atom, a hydroxyl group or a thiol group.

Among these, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4 '-Biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2' , 3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl) Methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene Acid dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride is preferred. Among these, in order to obtain a cured film with a tensile elongation of 50% or more and a tensile strength of 150 to 450 MPa, a 3,3' carboxylic acid residue structure in which two or more benzene rings are bonded with a single bond is required. , 4,4'-biphenyltetracarboxylic dianhydride, and 3,3',4,4'-biphenyltetracarboxylic dianhydride are preferable, and these acid anhydrides are combined with all the carboxylic acid residues contained in the polyimide precursor. It is preferable to use 50 to 100 mol%, assuming that the group is 100 mol%. Furthermore, it is more preferable to use bis(3,4-dicarboxyphenyl) ether dianhydride because a cured film with high elongation and excellent ablation processing can be obtained. Further, since cleavage of the polyimide precursor during curing can be suppressed, high elongation can be obtained even when the acid dianhydride residue is esterified, which is preferable.

R ⁶ in general formula (5) represents a divalent organic group, and represents an organic group derived from diamine.

Specific examples of diamine residues having an aromatic group include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, and 3,4'-diaminodiphenyl ether. '-Diamino diphenyl sulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4-bis(4-aminophenoxy)benzene, benzine, m- Phenylene diamine, p-phenylene diamine, 1,5-naphthalene diamine, 2,6-naphthalene diamine, bis(4-aminophenoxyphenyl) sulfone, bis(3-aminophenoxyphenyl) sulfone, bis(4-aminophenoxy) biphenyl , bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl- 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl Aromatic diamines such as -4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, and some of the hydrogen atoms of these aromatic rings and hydrocarbons. Examples include, but are not limited to, compounds in which the compound is substituted with an alkyl group having 1 to 10 carbon atoms, etc. The other diamine to be copolymerized can be used as it is or as a corresponding diisocyanate compound or trimethylsilylated diamine. Moreover, you may use these two or more types of diamine components in combination.

Among these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4, 4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 2,6-naphthalene Diamine, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, and 1,4-bis(4-aminophenoxy)benzene are preferred. Among these, in order to obtain a cured film with a tensile elongation of 50% or more and a tensile strength of 150 to 450 MPa, bis(3,3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, bis{4- It is preferable to use (4-aminophenoxy)phenyl}ether and 1,4-bis(4-aminophenoxy)benzene, and these diamines are used in an amount of 15 to 15%, assuming that the total diamine residues contained in the polyimide precursor are 100% by mole. It is preferable to use 98 mol%.Furthermore, it is more preferable to use 4,4'-diaminodiphenyl ether, since a cured film with high elongation and excellent ablation processing can be obtained.

Further, in order to obtain a cured film having a tensile strength of 150 to 450 MPa, the curing temperature of the resin composition is preferably 150°C to 350°C, more preferably 170°C to 200°C.

In the present invention, diamine residues and carboxylic acid residues containing a structure represented by general formula (1) are defined as 100 mol% of the total of all carboxylic acid residues and all amine residues contained in the polyimide precursor. It is preferable that the ratio of residues including acid residues is 10 to 99 mol%.

(In the general formula (1), R represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. a and b are integers of 0 to 4. * mark represents a bonding part.)
Examples of the organic group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an alkylene ether group, a fluoroalkyl group, and an aromatic group.
Note that the carboxylic acid residue and amine residue in the polyimide precursor include imidized sites.

The total of all carboxylic acid residues and all amine residues contained in the polyimide precursor is taken as 100 mol%, and the diamine residues and carboxylic acid residues containing the structure represented by general formula (1) are combined. It is preferable that the proportion of the residues is 10 mol % or more, since a cured film with high strength, high elongation and high adhesion can be obtained, as well as an absorbance suitable for ablation processing and a pattern with high resolution can be obtained. In addition, if the adhesion to the substrate is very high, even after ablation processing, a cured film that is difficult to remove tends to remain as a residue. The proportion of residues including groups is preferably 99 mol% or less.
From the viewpoint of pattern shape and balance of residue, 60 to 98 mol% is more preferable.

In addition, in the present invention, a diamine having an aliphatic group may be included, but since the film strength decreases and a residue is likely to be generated in the pattern during ablation processing, when copolymerizing as a diamine component, a polyimide precursor It is preferably 1 to 5 mol%, based on 100 mol% of all amine residues contained in the amine residues.

Examples of diamines having an aliphatic group include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-amino-phenyl)octamethylpentasiloxane, ethylenediamine, 1,3-diaminopropane, 2-methyl-1, 3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane , 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1 , 2-bis(2-aminoethoxy)ethane, KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, THF- 100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP-2005, RP-2009, RT-1000, HE-1000, HT-1100, Examples include HT-1700 (all product names, manufactured by HUNTSMAN Co., Ltd.).

Further, in the present invention, it is preferable that the resin (a) has an alicyclic diamine residue as well as a carboxylic acid residue structure in which two or more benzene rings are bonded by a single bond. Due to the carboxylic acid residue structure in which two or more benzene rings are bonded by single bonds, a cured film with high strength, high elongation, and high adhesion can be obtained, and the alicyclic diamine residue does not reduce the film strength. First, it is preferable because a high-resolution pattern with no residue can be obtained during ablation processing. In view of the balance between film strength and residue, the content ratio of alicyclic diamine residues is preferably 60 to 80 mol% with respect to the total amount of diamine residues of 100 mol%. The alicyclic diamine residue preferably has one or more structures selected from the group consisting of general formula (2), general formula (3), and general formula (4).

(In general formula (2), the * mark represents a bonding part.)

(In general formula (3), R ¹ and R ² may be the same or different, and each represents a hydrogen atom, a methyl group, or a trifluoromethyl group. In addition, m represents an integer within the range of 1 to 10. (In addition, the asterisk (*) represents the joint.)

(In general formula (4), R ³ and R ⁴ may be the same or different, and each represents a hydrogen atom, a methyl group, or a trifluoromethyl group. Also, the mark * represents a bonding part.)
Specifically, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1, Examples include 4-bis(aminomethyl)cyclohexane, 4,4'-methylenebis(cyclohexylamine), and 4,4'-methylenebis(2-methylcyclohexylamine).

In addition, diamines with phenolic hydroxyl groups may be used because strength can be improved by combining with a crosslinking agent, but if phenolic hydroxyl groups remain after curing, elongation will decrease and Since residues are likely to be generated in the pattern, when copolymerizing as a diamine component, 1 to 30 mol% of the total carboxylic acid residues and all amine residues contained in the polyimide precursor is taken as 100 mol%. preferable.

Specific examples of diamines having a phenolic hydroxyl group include bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, and bis(3-amino-4-hydroxyphenyl). Aromatic diamines such as hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, Compounds in which some of the hydrogen atoms of these aromatic rings and hydrocarbons are substituted with alkyl groups having 1 to 10 carbon atoms, and diamines having the structures shown below can be mentioned, but are not limited to these. Not done. The other diamine to be copolymerized can be used as it is or as a corresponding diisocyanate compound or trimethylsilylated diamine. Moreover, you may use these two or more types of diamine components in combination.

In general formula (5), R is preferably esterified with a hydrogen atom or an organic group having 1 to 20 carbon atoms, and the esterification rate of the carboxylic acid residue is preferably 10% or more and less than 90%. More preferred. Note that the carboxylic acid residue includes an imidized site. When imidization is 10%, the esterification rate is less than 90%.
By esterifying 10% or more of the carboxylic acid residues, ion migration during heat curing can be suppressed and adhesion can be imparted. When the polyimide precursor is esterified, the amount of carboxylic acid in the polyimide precursor decreases, and metal diffusion that occurs due to interaction between the carboxylic acid in the polyimide precursor and metal wiring during thermal curing is suppressed. . Therefore, the cured film has a low content of metal components, and a high-resolution pattern without residue can be obtained in ablation processing using a UV laser. It is also preferable in that a cured film with high physical properties can be obtained since cleavage of the polyimide precursor can be suppressed during thermal curing.

The esterification rate is more preferably 40% or more in view of the balance between metal adhesion, ablation residue, and shape.

Further, in the esterification, since the weight ratio of leaving groups remaining in the cured film is small, it is preferable to use an alkyl group or an alkyl ether group with a molecular weight of 100 or less. It is preferable that there are few leaving groups remaining in the cured film, since a cured film with high physical properties that can withstand ablation processing can be obtained, and a pattern with high resolution can be obtained. Specifically, in the above general formula (5), R is preferably a methyl group, an ethyl group, or a butyl group.

Regarding the above esterification, the compound represented by general formula (6) or general formula (7) is added in an amount of 130 mol % to 100 mol % of the total carboxylic acid residues of the structural units derived from the polyimide precursor structure. It is preferable to use 200 mol%. This is preferable since both esterification and imidization can be promoted.

(R ⁷ represents a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, and R ⁸ represents a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, a nitrogen-containing organic group, or an oxygen-containing organic group. ^R9 represents a monovalent organic group having 1 or more carbon atoms, and ^R10 represents any of a divalent cyclic organic group having 1 or more carbon atoms, a nitrogen-containing organic group, or an oxygen-containing organic group.)
In addition to the polyimide precursor structure, the resin (a) may be copolymerized with a polyamide structure, a polyhydroxyamide structure, a polybenzoxazole structure, a polybenzothiazole structure, etc., as long as the above properties are not lost.

Furthermore, the molar ratio of (a) resin in the present invention is confirmed by a method of detecting the peaks of the polyamide structure and polyimide structure in the obtained resin, resin composition, and cured film using a nuclear magnetic resonance apparatus (NMR). can. Note that if the molar ratio of the monomers used during polymerization is known, the molar ratio of the polyamide structure or polyimide structure can be calculated from the molar ratio of the monomers used during polymerization.

In the present invention, the resin (a) preferably has a weight average molecular weight of 3,000 to 200,000. Within this range, it is more preferably 30,000 to 100,000 or less in terms of high physical properties and ablation processability. The molecular weight can be measured by gel permeation chromatography (GPC) and converted from a standard polystyrene calibration curve.

In order to improve the storage stability of the resin composition of the present invention, the main chain end of the resin (a) is capped with other end-capping agents such as monoamines, monocarboxylic acids, acid anhydrides, and monoactive ester compounds. You may. Moreover, by sealing the ends of the resin (a) with an end-capping agent, the mechanical properties of the resulting cured film can be easily adjusted to a preferable range.

The introduction ratio of the terminal capping agent is preferably 0.1 mol% or more, more preferably 0.1 mol% or more based on the total amine component, in order to suppress the increase in the weight average molecular weight of the polyamide resin and the decrease in solubility in alkaline solutions. is 5 mol% or more. In addition, in order to suppress deterioration of the mechanical properties of the cured film obtained due to a decrease in the weight average molecular weight of the resin, the content is preferably 60 mol% or less, more preferably 50 mol% or less. Alternatively, a plurality of terminal capping agents may be reacted to introduce a plurality of different terminal groups.

Specifically, monoamines used as terminal capping agents include M-600, M-1000, M-2005, M-2070 (trade names manufactured by HUNTSMAN Co., Ltd.), aniline, 2-ethynylaniline, and 3-ethynyl. Aniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-amino Naphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid , 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2- Aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. can be used. Two or more types of these may be used.

Monocarboxylic acids and monoactive ester compounds as terminal capping agents include 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy -6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4 - Monocarboxylic acids such as carboxybenzenesulfonic acid and active ester compounds obtained by esterifying their carboxyl groups, phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, etc. acid anhydrides, dicarboxylic acids such as phthalic acid, maleic acid, nadic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, and tricarboxylic acids such as trimellitic acid and trimesine. Acid, diphenyl ether tricarboxylic acid, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene Active ester compounds obtained by the reaction of one carboxyl group of dicarboxylic acids such as N-hydroxybenzotriazole, imidazole, N-hydroxy-5-norbornene-2,3-dicarboximide, and their aromatic rings and carbonization. Compounds in which some of the hydrogen atoms of hydrogen are substituted with an alkyl group having 1 to 10 carbon atoms can be used. Two or more types of these may be used.

The terminal capping agent that can be used in the present invention can be easily detected by the following method. For example, the resin (a) into which the terminal capping agent has been introduced is dissolved in an acidic solution, decomposed into the constituent units of amine component and acid anhydride component, and then analyzed by gas chromatography (GC) or NMR. The terminal capping agent used in the present invention can be easily detected. Apart from this, it can also be easily detected by directly measuring the resin component (a) into which the terminal capping agent has been introduced using pyrolysis gas chromatography (PGC), infrared spectrum, and ¹³ C-NMR spectrum.

In the present invention, the resin (a) is synthesized, for example, by the following method, but is not limited thereto.

The polyimide precursor structure is created by first dissolving the diamine, acid dianhydride, and other copolymer components in an organic solvent at room temperature, or at an elevated temperature in some cases, and then heating to polymerize. From the viewpoint of stability of the solution during the reaction, it is preferable to dissolve the diamine compound with higher solubility first. In some cases, other copolymerization components are added, and an acid, an acid anhydride, or a monoamine serving as a terminal capping agent is added and polymerized.

When the obtained polyimide precursor is esterified, carboxylic acid is reacted with an esterifying agent after the above polymerization. In particular, when general formula (6) or general formula (7) is used, the imidization rate can be adjusted.

Further, the imidization of the resin (a) of the present invention may be adjusted by adding an imidization promoter such as pyridine and stirring at 40 to 150°C.

In the present invention, (a) resin may be polymerized by the above method and then mixed with other additives to form a resin composition. It is preferable to filter, dry, and isolate. The drying temperature is preferably 40 to 100°C, more preferably 50 to 80°C. This operation removes unreacted monomers and oligomer components such as dimers and trimers, thereby improving the film properties after heat curing.

The imidization rate in the present invention can be easily determined, for example, by the following method. First, the infrared absorption spectrum of the polymer is measured to confirm the presence of absorption peaks (around 1780 cm ^-1 and around 1377 cm ^-1 ) of the imide structure caused by polyimide. Next, we measured the infrared absorption spectrum of the polymer heat-treated at 350°C for 1 hour as a sample with an imidization rate of 100%, and compared the peak intensities around 1377 cm ^-1 of the resin before and after the heat treatment. The content of imide groups in the pre-resin is calculated and the imidization rate is determined.

Examples of organic solvents used for resin polymerization include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N,N' - Dimethylpropylene urea, N,N-dimethylisobutyric acid amide, amides of methoxy-N,N-dimethylpropionamide, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α- Cyclic esters such as methyl-γ-butyrolactone, carbonates such as ethylene carbonate and propylene carbonate, glycols such as triethylene glycol, phenols such as m-cresol and p-cresol, acetophenone, 1,3-dimethyl-2 - Examples include, but are not limited to, imidazolidinone, sulfolane, dimethyl sulfoxide, tetrahydrofuran, dimethyl sulfoxide, propylene glycol monomethyl ether acetate, ethyl lactate, and the like.

The resin composition of the present invention contains (b) a solvent. As a solvent, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2 - Polar aprotic solvents such as imidazolidinone, N,N'-dimethylpropylene urea, N,N-dimethylisobutyric acid amide, methoxy-N,N-dimethylpropionamide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene Ethers such as glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate Examples include alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, and 3-methyl-3-methoxybutanol, and aromatic hydrocarbons such as toluene and xylene. Two or more types of these may be contained.

The content of the solvent is preferably 100 parts by mass or more per 100 parts by mass of (a) resin in order to dissolve the resin, and 1,500 parts in order to form a coating film with a thickness of 1 μm or more. It is preferable that the content is less than 1 part by mass.

It is preferable that the resin composition of the present invention further contains (c) a basic additive. (c) By containing a basic additive, high imidization is possible, and high physical properties of the film are obtained, resulting in a highly reliable cured film and a high-resolution pattern with no residue during ablation processing. is obtained. This is because the basic additive coordinates around the imide groups, suppressing polymer aggregation in the cured film, and as a result, bonds between molecules and atoms of the polymer are instantly broken during ablation processing with a UV laser. This is thought to be because decomposition, vaporization, and transpiration occur uniformly.
(c) Basic additives include imidazole, pyrazole, triazole, tetrazole, benzimidazole, naphthoimidazole, indazole, benzotriazole, purine, imidazoline, pyrazoline, pyridine, quinoline, isoquinoline, dipyridyl, diquinolyl, pyridazine, pyrimidine, pyrazine. , phthalazine, quinoxaline, quinazoline, cinnoline, naphthyridine, acridine, phenanthridine, benzoquinoline, benzisoquinoline, benzocinnoline, benzophthalazine, benzoquinoxaline, benzoquinazoline, phenanthroline, phenazine, carboline, perimidine, triazine, tetrazine, pteridine, oxazole , benzoxazole, isoxazole, benzisoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, oxadiazole, thiadiazole, pyrroledione, isoindoledione, pyrrolidinedione, benzisoquinolinedione, triethylenediamine, and hexamethylenetetramine , some of the hydrogen atoms of these aromatic rings, heterocycles, hydrocarbons and hydrogen nitrides are replaced with di-substituted amino groups (dimethylamino group, diethylamino group, dibutylamino group, ethylmethylamino group, butylmethylamino group, diamylamino group). group, dibenzylamino group, diphenethylamino group, diphenylamino group, ditolylamino group, dixylylamino group, methylphenylamino group, benzylmethylamino group, etc.), monosubstituted amino group (methylamino group, ethylamino group, propyl Amino group, isopropylamino group, tert-butylamino group, anilino group, anisidino group, phenetidino group, toluidino group, xylidino group, pyridylamino group, thiazolyl amino group, benzylamino group, benzylidene amino group, etc.), cyclic amino group (pyrrolidino group) , piperidino group, piperazino group, morpholino group, 1-pyrrolyl group, 1-pyrazolyl group, 1-imidazolyl group, 1-triazolyl group, etc.), acylamino group (formylamino group, acetylamino group, benzoylamino group, cinnamoylamino group) group, pyridinecarbonylamino group, trifluoroacetylamino group), sulfonylamino group (mesylamino group, ethylsulfonylamino group, phenylsulfonylamino group, pyridylsulfonylamino group, tosylamino group, taurylamino group, trifluoromethylsulfonylamino group, sulfamoylamino group, methylsulfamoylamino group, sulfanylamino group, acetylsulfanylamino group), amino group, hydroxyamino group, ureido group, semicarbazide group, carbazido group, disubstituted hydrazino group (dimethylhydrazino group, diphenylhydrazino group, methylphenylhydrazino group, etc.), monosubstituted hydrazino group (methylhydrazino group, phenylhydrazino group, pyridylhydrazino group, benzylidenehydrazino group, etc.), hydrazino group, amidino group, hydroxyl group, oxime groups (hydroxyiminomethyl group, methoxyiminomethyl group, ethoxyiminomethyl group, hydroxyiminoethyl group, hydroxyiminopropyl group, etc.), hydroxyalkyl group (hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, etc.), hydroxyaryl group (hydroxyphenyl group, hydroxynaphthyl group, dihydroxyphenyl group, etc.), alkoxyalkyl group (methoxymethyl group, methoxyethyl group, ethoxyethyl group, etc.), cyano group, cyanato group, thiocyanato group, nitro group, nitroso group, oxy group (methoxy group, ethoxy group, propoxy group, butoxy group, hydroxyethoxy group, phenoxy group, naphthoxy group, pyridyloxy group, thiazolyloxy group, acetoxy group, etc.), thio group (methylthio group, ethylthio group, phenylthio group, pyridylthio group, thiazolylthio group, etc.), mercapto group, halogen group (fluoro group, chloro group, bromo group, iodo group), carboxyl group and its salts, oxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, pyridyloxycarbonyl group) ), aminocarbonyl groups (carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, pyridylcarbamoyl group, carbazoyl group, allophanoyl group, oxamoyl group, succinamoyl group, etc.), thiocarboxyl group and its salts, dithiocarboxyl group and its salts, Thiocarbonyl groups (methoxythiocarbonyl group, methylthiocarbonyl group, methylthiothiocarbonyl group, etc.), acyl groups (formyl group, acetyl group, propionyl group, acryloyl group, benzoyl group, cinnamoyl group, pyridinecarbonyl group, thiazolecarbonyl group, fluoroacetyl group, etc.), thioacyl group (thioformyl group, thioacetyl group, thiobenzoyl group, pyridinethiocarbonyl group, etc.), sulfinic acid group and its salts, sulfonic acid group and its salts, sulfinyl group (methylsulfinyl group, ethylsulfinyl group) , phenylsulfinyl group, etc.), sulfonyl group (mesyl group, ethylsulfonyl group, phenylsulfonyl group, pyridylsulfonyl group, tosyl group, tauryl group, trifluoromethylsulfonyl group, sulfamoyl group, methylsulfamoyl group, sulfanylyl group, acetyl group) sulfanylyl group, etc.), oxysulfonyl group (methoxysulfonyl group, ethoxysulfonyl group, phenoxysulfonyl group, acetaminophenoxysulfonyl group, pyridyloxysulfonyl group, etc.), thiosulfonyl group (methylthiosulfonyl group, ethylthiosulfonyl group, phenyl thiosulfonyl group, acetaminophenylthiosulfonyl group, pyridylthiosulfonyl group), aminosulfonyl group (sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, phenyl sulfamoyl group, acetaminophenylsulfamoyl group, pyridylsulfamoyl group, etc.), ammonio group (trimethylammonio group, ethyldimethylammonio group, dimethylphenylammonio group, pyridinio group, quinolinio group, etc.) groups (phenylazo group, pyridylazo group, thiazolyl azo group, etc.), azoxy group, halogenated alkyl group (chloromethyl group, bromomethyl group, fluoromethyl group, dichloromethyl group, dibromomethyl group, difluoromethyl group, trifluoromethyl group, penta fluoroethyl group, heptafluoropropyl group, etc.), hydrocarbon group (alkyl group, aryl group, alkenyl group, alkynyl group, etc.), heterocyclic group, organosilicon group (silyl group, disilanyl group, trimethylsilyl group, triphenylsilyl group) etc.), but is not limited thereto. Two or more types of these may be contained.

Among these, the basic additive (c) preferably has a pH of 9.5 to 11.5. In the present invention, the pH value is a value measured in a 10% aqueous solution at room temperature using an aqueous solution pH measurement method using a gas electrode (JISZ-8802, 1984).

(c) When the basic additive has a pH of 9.5 or higher, coordination to imide groups occurs, which makes it easier to suppress polymer aggregation within the cured film and suppress residues during ablation processing, resulting in high resolution. It is preferable because In addition, (c) if the basicity of the basic additive is too high, the basic additive acts on multiple polymers, which strengthens the interaction between the polymers and similarly tends to cause polymer aggregation. is preferably 11.5 or less.
Furthermore, the basic additive (c) is preferably an imidazole derivative having two or more substituents. Examples of the substituent include an alkyl group, an alkylene ether group, a fluoroalkyl group, an aromatic group, an amide group, a carbonyl group, and an alkylamino group. By having two or more substituents, the imidazole derivative can coordinate to the imide group while inhibiting the interaction of multiple polymers, thereby suppressing aggregation during ablation processing and achieving even higher resolution. This is preferable because a pattern can be obtained.

Specifically, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, and 1-methyl-4-ethylimidazole, 1-methoxycarbonylaminomethylimidazole, 1- (2-methoxycarbonylaminoethyl)-2-methylimidazole, 1-(2-ethoxycarbonylaminoethyl)-2-methylimidazole, 1-(2-propoxycarbonylaminoethyl)-2-methylimidazole, 1-(2 -butoxycarbonylaminoethyl)-2-methylimidazole, 1-(2-phenoxycarbonylaminoethyl)-2-methylimidazole, 1-(3-methoxycarbonylaminopropyl)-2-methylimidazole, 1-(3-ethoxy carbonylaminopropyl)-2-methylimidazole, 1-(3-propoxycarbonylaminopropyl)-2-methylimidazole, 1-(3-butoxycarbonylaminopropyl)-2-methylimidazole, 1-(3-phenoxycarbonylamino propyl)-2-methylimidazole, 1-(2-methoxycarbonylaminoethyl)-2-phenylimidazole, 1-(3-methoxycarbonylaminopropyl)-2-phenylimidazole, 1-(2-aminoethyl)-2 -Methylimidazole, 1-(3-aminopropyl)-2-methylimidazole, 1-(2-aminoethyl)-2-phenylimidazole, 1-(3-aminopropyl)-2-phenylimidazole, 1-(3 Examples include, but are not limited to, -aminopropyl)-2-undecylimidazole, 1-[2-(methylamino)ethyl]-2-phenylimidazole, and the like.

The amount of the basic additive (c) added is preferably 0.01 to 50 parts by weight, more preferably 0.05 to 10 parts by weight, and more preferably 0.1 to 1. 5 parts by mass is particularly preferred. This range is preferable because the effects of the basic additive (c) can be obtained and the resin composition has excellent storage stability.

The resin composition of the present invention further contains (d) a crosslinking agent, and it is preferable that the (d) crosslinking agent has three or more methylol groups or alkoxymethyl groups.
(d) The crosslinking agent crosslinks between polymers in the cured film, thereby suppressing aggregation of imide groups in the cured film, thereby suppressing residues and obtaining a high-resolution pattern, which is preferable.

Examples include MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (trade names, manufactured by Sanwa Chemical Co., Ltd.) and the following cross-linked Examples include, but are not limited to, agents. Two or more types of these may be contained.

(In the formula, c, d, and e each represent an integer of 1 or more, and preferably 3≦c≦20, 1≦d≦30, and 1≦e≦30.)
Further, the content of the crosslinking agent (d) relative to 100 parts by mass of the resin (a) is preferably within the range of 15 to 70 parts by mass. When the amount is 15 parts by mass or more, high density of the cured film and antioxidant effect can be obtained, and a decrease in elongation after reliability evaluation can be greatly suppressed. When the amount is 70 parts by mass or less, the elongation of the cured film can be improved, cracks in the film can be reduced, and adhesion to metal wiring can also be improved.

It is preferable that the resin composition of the present invention further contains (e) a surfactant. This makes the surface thickness of the cured film uniform, so the refractive index of the surface becomes uniform, and a high-resolution pattern can be obtained during laser processing.

Specifically, as the surfactant, "Florado" (registered trademark) manufactured by Sumitomo 3M Co., Ltd., D
Fluorine surfactants such as “Megafac” (registered trademark) manufactured by IC Corporation and “Sulfuron” (registered trademark) manufactured by Asahi Glass Co., Ltd., KP341 manufactured by Shin-Etsu Chemical Co., Ltd., and Chisso Corporation Organic siloxane surfactants such as DBE manufactured by Kyoeisha Chemical Co., Ltd., “Polyflow” (registered trademark) and “Granol” (registered trademark) manufactured by Kyoeisha Chemical Co., Ltd., BYK manufactured by BYK Chemie Co., Ltd.,
Examples include acrylic polymer surfactants such as Polyflow manufactured by Co., Ltd. Among these, (a) acrylic polymer surfactants are preferred because they tend to be unevenly distributed on the surface of the cured film due to their low compatibility with the resin. The surfactant is preferably contained in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the heat-resistant resin precursor.

The resin composition of the present invention may contain a photosensitizer to the extent that no residue is generated during ablation processing and the physical properties are not deteriorated. When a photosensitive resin composition contains a photosensitive agent such as a naphthoquinone diazide compound, a polymerization initiator, or a photopolymerizable compound, reactions and foaming may occur during laser processing, resulting in processing failure or residue generation. Occur. Furthermore, the photosensitive agent is a monomer component, and if it remains in the cured film, it is not preferable because the film properties after reliability will deteriorate.

In addition, in order to improve the adhesion to the substrate, the resin composition of the present invention may contain trimethoxyaminopropylsilane, trimethoxyepoxysilane, trimethoxyvinylsilane, trimethoxythiolpropyl as a silicone component within a range that does not impair storage stability. It may contain a silane coupling agent such as silane.

The preferable content of the silane coupling agent is 0.01 to 5 parts by weight based on 100 parts by weight of the resin (a).

The resin composition of the present invention may contain other resins as long as the properties of (a) resin are not impaired, but non-fluorine resins are preferred. Fluorine resins include polytetrafluoroethylene, trichlorofluoroethylene, tetrafluoroethylene-hexafluoropropylene, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene-perfluoroalkyl vinyl ether, tetrafluoroethylene-ethylene, and chlorotrifluoroethylene. - means ethylene resin. Fluorine does not absorb in the ultraviolet region, so even if it contains resin or additives that absorb in the ultraviolet region, it cannot be removed and a residue is generated when forming fine patterns during ablation processing. However, since interactions with molecular chains and metals are suppressed, physical properties and adhesion are reduced, so a non-fluororesin is preferable.

Examples of other resins include polyimide resins, polybenzoxazole, polybenzoxazole precursors, polyamide resins, siloxane resins, acrylic polymers copolymerized with acrylic acid, epoxy resins, novolak resins, resol resins, and polyhydroxy resins. Examples include styrene resins, modified products having crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups introduced therein, and copolymers thereof.

The viscosity of the resin composition of the present invention is preferably 2 to 5,000 mPa·s. Viscosity can be measured using an E-type rotational viscometer. By adjusting the solid content concentration so that the viscosity is 2 mPa·s or more, it becomes easy to obtain a desired film thickness. On the other hand, if the viscosity is 5,000 mPa·s or less, it becomes easy to obtain a highly uniform coating film. A resin composition having such a viscosity can be easily obtained, for example, by adjusting the solid content concentration to 5 to 60% by mass.

Next, a method for forming a relief pattern of a cured film using the resin composition of the present invention will be described.

First, the resin composition of the present invention is applied to a substrate. Substrates include silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, composite boards of silicon wafers and sealing resins such as epoxy resin, and circuit constituent materials placed on these boards. Examples include, but are not limited to:

Examples of organic circuit boards include glass substrate copper clad laminates such as glass cloth/epoxy copper clad laminates, composite copper clad laminates such as glass nonwoven fabric/epoxy copper clad laminates, temporary carrier substrates, and polyetherimide. Examples include heat-resistant/thermoplastic substrates such as resin substrates, polyetherketone resin substrates, and polysulfone resin substrates, and flexible substrates such as polyester copper-clad film substrates and polyimide copper-clad film substrates. Examples of inorganic circuit boards include ceramic substrates such as glass substrates, alumina substrates, aluminum nitride substrates, and silicon carbide substrates, and metal substrates such as aluminum-based substrates and iron-based substrates. Examples of circuit constituent materials include conductors containing metals such as silver, gold, and copper, resistors containing inorganic oxides, low dielectric materials containing glass materials and/or resins, resins and high Examples include high dielectric materials containing dielectric constant inorganic particles, and insulators containing glass-based materials.

Silicon wafers have high absorption at UV wavelengths, and organic circuit boards have absorption bands close to those of polyimide, so when laser processing is performed, they are likely to be patterned together with the cured film, making it difficult to form the desired pattern. For this reason, it is preferable that metal wiring with high reflection at UV wavelengths be formed on the base of the part where the cured film is processed.

As for the metal wiring, since the surface state changes by air oxidation, it is preferable to perform an oxidation treatment in advance using oxygen plasma treatment, hydrogen peroxide solution, or the like.

Application methods include spin coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, screen coater, and slit die coater. Examples include methods such as tar. The thickness of the coating film varies depending on the coating method, solid content concentration of the composition, viscosity, etc., but the coating is usually done so that the film thickness after drying is 0.1 to 150 μm. If it is an uncured sheet, it is then dried and peeled off.

In order to improve the adhesion between a substrate such as a silicon wafer and the resin composition, the substrate can also be pretreated with the above-mentioned silane coupling agent. For example, a solution in which 0.5 to 20% by mass of a silane coupling agent is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. , surface treatment by spin coating, dipping, spray coating, steam treatment, etc. In some cases, heat treatment is then performed at 50° C. to 300° C. to advance the reaction between the substrate and the silane coupling agent.

Next, the resin composition or uncured sheet is applied or laminated onto the substrate, and the substrate is dried to obtain a resin composition coating. Drying is preferably carried out using an oven, hot plate, infrared rays, etc. at a temperature of 50° C. to 180° C. for 1 minute to several hours.

The heat treatment in the present invention, that is, the curing conditions, is preferably 150°C or more and 350°C or less. The temperature is more preferably 170°C or more and 200°C or less in order to avoid any influence on the substrate/semiconductor device and to obtain appropriate elongation/strength.

The elongation at break of the cured film obtained by curing the resin composition of the present invention is preferably 50% or more, more preferably 100% or more. Further, the strength is preferably 150 MPa or more and 450 MPa or less, more preferably 180 MPa or more and 300 MPa or less. Within this range, decomposition and deterioration of the cured film at the pattern processing interface during laser irradiation can be suppressed, and if the tensile strength is 450 MPa or less, pattern processing is possible even if the energy irradiation time is short, so the shape can be Fine patterns can be formed without causing abnormalities. Therefore, a fine pattern that can withstand reliability evaluation can be obtained.

An interlayer insulating film that is in contact with various materials is easily subjected to loads due to differences in thermal expansion coefficients, so materials with higher elongation and higher strength are required. Materials with high elongation and low strength tend to change their elongation during reliability tests such as thermal cycle tests, and materials with low elongation and high strength are rigid and therefore prone to cracking. Further, since the smaller the difference in thermal expansion coefficient, the lower the load itself can be, it is preferable that the thermal expansion coefficient of the formed material is close to that of the cured film. The cured film obtained by curing the resin composition of the present invention has high elongation and high strength, and also has high metal adhesion, so it is possible to avoid cracks in the multilayer cured film or peeling from metal wiring during reliability evaluation. is unlikely to occur. Reliability evaluations include impact tests, high temperature retention tests, constant temperature and high humidity tests, and thermal cycle tests. A cured film obtained by curing the resin composition of the present invention can be used for electronic components such as semiconductor devices and multilayer wiring boards. Specifically, it is suitably used for applications such as passivation films for semiconductors, surface protection films for semiconductor elements, interlayer insulating films, interlayer insulating films for multilayer wiring for high-density packaging, and insulating layers for organic electroluminescent devices. It is not limited to , and can take various structures. Among these, it is preferable to use it as a multilayer wiring for high-density packaging and as an interlayer insulating film using rewiring. This is because rewiring structures use a wide variety of materials and require different patterns compared to applications such as circuit boards, but cracks and peeling may occur when packaged. This is because materials that have high elongation, high strength, and can form fine patterns are sought after.

The cured film is subjected to ablation processing by irradiating it with UV laser in order to form a pattern at a desired position. The irradiation conditions for this UV laser are not particularly limited, but excimer lasers such as ArF (193 nm), KrF (248 nm), XeCl (308 nm), and XeCl (351 nm), and YAG laser (355 nm) are usually used. It will be done. Among these, excimer laser is preferable because it does not apply much heat during processing and can form a high-resolution pattern with a via diameter of 5 μm or less, and the cured film can obtain an appropriate absorbance at the wavelength of the UV laser, so Processing using KrF (248 nm) is more preferable because a high-resolution pattern without residue can be obtained.

When forming a pattern, the UV laser beam with an energy density of 5 to 10,000 mJ/cm ² is applied directly or as desired at a repetition pulse rate of 1 to 3,000 Hz through an optical system with a reduction magnification of 0.1 to 20 times. A pattern can be formed by irradiating the cured film forming substrate for a predetermined time using a patterning mask having the shape of .

The cured film of the resin base composition of the present invention can be obtained in a rectangular tapered shape by setting the UV laser irradiation energy to 500 to 1000 mJ/cm ² and controlling the energy density to 100 or more and less than 500 mJ/cm ² This is preferable because the taper shape can be controlled.

Therefore, the cured film obtained from the resin composition of the present invention is different from that of negative photosensitive resin compositions that tend to be rectangular and positive photosensitive resin compositions that are susceptible to reflow and tend to have a smooth shape. Therefore, it is easy to control the taper shape. This is preferable because the shape can be easily controlled in an interlayer insulating film where each layer requires a different shape due to different wiring thicknesses and pattern formation densities.

In the present invention, the absorbance of the cured film when the resin composition is cured is preferably 0.07 to 0.9 per 1 μm of film thickness at the wavelength of the UV laser, and preferably 0.1 to 0.3. It is even more preferable. This range is preferable because pattern formation is possible with the UV laser and abnormalities in shape that occur due to too high absorbance do not occur.

Next, an example of application of the resin composition of the present invention to a semiconductor device having bumps will be described with reference to the drawings (Application Example 1). FIG. 1 is an enlarged sectional view of a pad portion of a semiconductor device having bumps according to the present invention. As shown in FIG. 1, a passivation film 3 is formed on a silicon wafer 1 on an input/output aluminum (hereinafter referred to as Al) pad 2, and a via hole is formed in the passivation film 3. Furthermore, an insulating film 4 is formed as a pattern using the resin composition of the present invention on this, and furthermore, a metal (Cr, Ti, etc.) film 5 is formed so as to be connected to the Al pad 2, and a metal film 4 is formed by electrolytic plating or the like. Wiring (Al, Cu, etc.) 6 is formed. A metal film (Cr, Ti, etc.) 5 is etched around the solder bump 10 to provide insulation between each pad. Further, an insulating film 7 is formed thereon as a pattern using the resin composition of the present invention. A barrier metal 8 and a solder bump 10 are formed on the insulated pad. The resin of the present invention has excellent elongation and strength, so by deforming the resin itself, it can relieve the stress from the sealing resin during mounting, thereby preventing damage to bumps, wiring, and low-k layers. Highly reliable semiconductor devices can be provided.

Next, a detailed method for manufacturing the semiconductor device will be described in FIG. As shown in FIG. 2A, an input/output Al pad 2 and a passivation film 3 are formed on a silicon wafer 1, and an insulating film 4 is formed as a pattern using the resin composition of the present invention. Next, as shown in 2b of FIG. 2, a metal (Cr, Ti, etc.) film 5 is formed so as to be connected to the Al pad 2, and as shown in 2c of FIG. ) 6 is formed by plating. Next, as shown in 2d' in FIG. 2, the resin composition of the present invention is applied, cured, and then subjected to ablation processing to form the insulating film 7 in a pattern as shown in 2d in FIG. . Further wiring (so-called rewiring) can be formed on the insulating film 7. When forming a multilayer wiring structure with two or more layers, the above steps are repeated to form a multilayer wiring structure in which two or more layers of rewiring are separated by an interlayer insulating film obtained from the resin composition of the present invention. structure can be formed. At this time, the formed insulating film comes into contact with various chemical solutions multiple times, but since the insulating film obtained from the resin composition of the present invention has excellent adhesion, it can form a good multilayer wiring structure. can be formed. Although there is no upper limit to the number of layers in a multilayer wiring structure, those having 10 layers or less are often used. At this time, the resin composition of the insulating film 7 is subjected to thick film processing at the scribe line 9. When forming a multilayer wiring structure of three or more layers, the above steps can be repeated to form each layer.

Next, as shown in 2e and 2f of FIG. 2, barrier metal 8 and solder bumps 10 are formed. Then, it is diced along the last scribe line 9 and cut into chips.

Next, Application Example 2 to a semiconductor device having bumps using the resin composition of the present invention will be described with reference to the drawings. FIG. 3 is an enlarged sectional view of a pad portion of a semiconductor device having an insulating film according to the present invention, and has a structure called a fan-out wafer level package (fan-out WLP). Similarly to Application Example 1 above, the silicon wafer 1 on which the Al pad 2 and the passivation film 3 are formed is diced and cut into chips, and then sealed with a resin 11. An insulating film 4 is formed as a pattern using the resin composition of the present invention over the sealing resin 11 and the chip, and furthermore, a metal (Cr, Ti, etc.) film 5 and metal wiring 6 are formed. Thereafter, barrier metal 8 and solder bumps 10 are formed in the openings of insulating film 7 formed on the sealing resin outside the chip. Fan-out WLP involves providing an extended portion around a semiconductor chip using a sealing resin such as epoxy resin, rewiring from the electrodes on the semiconductor chip to the extended portion, and mounting solder balls on the extended portion as well. This is a semiconductor package that has the required number of terminals. In fan-out WLP, wiring is installed so as to straddle the boundary line formed between the main surface of the semiconductor chip and the main surface of the sealing resin. That is, an interlayer insulating film is formed on a base material made of two or more materials: a semiconductor chip with metal wiring and a sealing resin, and the wiring is formed on the interlayer insulating film.

In addition, fan-out WLP is arranged as an interlayer insulating film between rewirings on a support substrate on which a temporary attachment material is placed, and after placing a silicon chip and a sealing resin on it, a support substrate on which a temporary attachment material is placed. There is a type of package that is created using a process called RDL-first, which separates the substrate and rewiring.

A method for manufacturing a semiconductor device using RDL first will be described with reference to FIG. In 3a of FIG. 5, a barrier metal such as Ti is formed on the supporting substrate 20 by a sputtering method, a Cu seed (seed layer) is formed thereon by a sputtering method, and then an electrode pad 21 is formed by a plating method. In the subsequent step 3b, a patterned insulating film 22 is formed by applying the resin composition of the present invention, curing it, and then performing an ablation process. Then, in step 3c, a seed layer is formed again by sputtering, and metal wiring 23 (rewiring layer) is formed by plating. Thereafter, in order to match the pitch of the conductive parts of the semiconductor chip with the pitch of the metal wiring, steps 3b and 3c are repeated to form a multilayer wiring structure as shown in 3d. Next, in step 3e, the photosensitive resin composition of the present invention is applied again, and after curing, ablation processing is performed to form a patterned insulating film, and then Cu posts 24 are formed by plating. Here, the pitch of the Cu posts and the pitch of the conductive parts of the semiconductor chip are equal. That is, in order to make the rewiring layer multilayer while narrowing the metal wiring pitch, the thickness of the interlayer insulating film is determined as follows: interlayer insulating film 1>interlayer insulating film 2>interlayer insulating film 3>, as shown in 3e of FIG. Interlayer insulating film 4>. Next, in step 3f, the semiconductor chip 26 is connected via the solder bumps 25, and an RDL first semiconductor device having a multilayer wiring structure can be obtained. In addition to this, in a type of semiconductor package in which the semiconductor chip is embedded in a recess formed in a glass epoxy resin substrate, wiring is installed so as to straddle the boundary line between the main surface of the semiconductor chip and the main surface of the printed circuit board. . Also in this embodiment, an interlayer insulating film is formed on a base material made of two or more types of materials, and wiring is formed on the interlayer insulating film. The cured film formed by curing the resin composition of the present invention has high elongation and high adhesion to semiconductor chips with metal wiring, as well as high adhesion to epoxy resins and other sealing resins. Therefore, it is suitably used as an interlayer insulating film provided on a base material made of two or more types of materials.

Further, in fan-out WLP, rewiring is becoming finer. The cured film of the resin composition of the present invention has high metal adhesion even to wires with a width of metal wires and an interval between adjacent wires of 5 μm or less, and therefore is suitable for use in fine rewiring.

In this structure, the thickness of the interlayer insulating film becomes thinner as it approaches the semiconductor chip, and as the redistribution layer approaches the semiconductor chip, the width of the metal wiring and the spacing between adjacent wirings become narrower. This makes it compatible with higher chip integration. For this reason, high elongation, high strength, and fine pattern processing have become important issues.

Next, Application Example 3 to coil parts of an inductor device using the resin composition of the present invention will be described with reference to the drawings. FIG. 4 is a sectional view of a coil component having an insulating film according to the present invention. As shown in FIG. 4, an insulating film 13 is formed on the substrate 12, and an insulating film 14 is formed thereon as a pattern. As the substrate 12, ferrite or the like is used. The resin composition of the present invention may be used for either the insulating film 13 or the insulating film 14. A metal (Cr, Ti, etc.) film 15 is formed in the opening of this pattern, and a metal wiring (Ag, Cu, etc.) 16 is plated thereon. The metal wiring 16 (Ag, Cu, etc.) is formed spirally. By repeating steps 13 to 16 multiple times and stacking layers, it is possible to provide a function as a coil. Finally, the metal wiring 16 (Ag, Cu, etc.) is connected to the electrode 18 by a metal wiring 17 (Ag, Cu, etc.) and sealed with a sealing resin 19.

The resin composition of the present invention is also suitably used for organic EL display devices. The organic EL display device has a drive circuit, a planarizing layer, a first electrode, an insulating layer, a light emitting layer, and a second electrode on a substrate, and the planarizing layer and/or the insulating layer are made of the cured film of the present invention. Become. In recent years, organic EL display devices are required to maintain high temperatures of about 100° C. or to have durability in reliability evaluations such as thermal cycle tests. Since the cured film of the present invention has high elongation and high adhesion to metal wiring and metal electrodes even after these reliability evaluations, stable driving and light emission characteristics can be obtained. For example, an active matrix display device has a TFT on a substrate made of glass or various plastics, and wiring located on the side of the TFT and connected to the TFT, and covering unevenness on top of the TFT. In this manner, a flattening layer is provided, and a display element is further provided on the flattening layer. The display element and the wiring are connected through contact holes formed in the planarization layer.

FIG. 6 shows a cross-sectional view of an example of a TFT substrate. Bottom-gate or top-gate TFTs (thin film transistors) 1 are provided in a matrix on a substrate 32 , and an insulating layer 29 is formed to cover the TFTs 27 . Further, on this insulating layer 29, a wiring 28 connected to the TFT 27 is provided. Furthermore, a planarization layer 30 is provided on the insulating layer 29 so as to embed the wiring 28 therein. A contact hole 33 that reaches the wiring 28 is provided in the planarization layer 30 . An ITO (transparent electrode) 31 is formed on the planarization layer 30 while being connected to the wiring 28 through the contact hole 33 . Here, the ITO 31 becomes an electrode of a display element (for example, an organic EL element). Then, an insulating layer 34 is formed to cover the periphery of the ITO 31. The organic EL element may be of a top emission type that emits light from the side opposite to the substrate 32, or may be of a bottom emission type that extracts light from the side of the substrate 32. In this way, an active matrix type organic EL display device is obtained in which each organic EL element is connected to a TFT 27 for driving the organic EL element.

The insulating layer 29, the planarization layer 30, and/or the insulating layer 34 are formed by forming a photosensitive resin film made of the resin composition or resin sheet of the present invention as described above, exposing the photosensitive resin film to light, It can be formed by a step of developing an exposed photosensitive resin film and a step of heat-treating the developed photosensitive resin film. An organic EL display device can be obtained by a manufacturing method including these steps.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. First, evaluation methods in each example and comparative example will be explained. For the evaluation, resin compositions (hereinafter referred to as varnishes) prepared in Examples and Comparative Examples that had been filtered in advance with a 1 μm polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) were used.

(1) Molecular weight measurement, imidization rate, esterification rate measurement (a) The weight average molecular weight (Mw) of the resin was measured using a GPC (gel permeation chromatography) device Waters 2690-996 (manufactured by Nippon Waters Co., Ltd.). confirmed. The developing solvent was measured as N-methyl-2-pyrrolidone (hereinafter referred to as NMP), and the weight average molecular weight (Mw) and dispersity (PDI=Mw/Mn) were calculated in terms of polystyrene.

Regarding the imidization rate of the resin, a solution of the resin dissolved in n-methylpyrrolidone was spin-coated onto a silicon wafer, dried at 120°C for 3 minutes, and then dried in an inert oven CLH-21CD-S (Koyo Thermo System). Co., Ltd.), the temperature was raised to 170°C at a rate of 3.5°C/min at an oxygen concentration of 20 ppm or less, and heat treatment was performed at 170°C for 1 hour. Furthermore, an infrared absorption spectrum was measured, and the presence of absorption peaks of the imide structure (around 1780 cm ⁻¹ and around 1377 cm ⁻¹ ) was confirmed. Next, the coating film was heat-treated at 350°C for 1 hour, and the infrared absorption spectrum was measured using a sample with an imidization rate of 100%, and the peak intensities near 1377 cm ^-1 of the resin before and after the heat treatment were compared. The content of imide groups in the resin before heat treatment was calculated, and the imidization rate was determined. For the measurement of the infrared absorption spectrum, "FT-720" (trade name, manufactured by Horiba, Ltd.) was used as a measuring device.

In addition, the esterification rate of the resin was measured in a deuterated dimethyl sulfoxide solution using a 400 MHz, ¹ H-NMR (nuclear magnetic resonance) device (AL-400, manufactured by JEOL Ltd.) with a total number of 16 times. The esterification rate was calculated based on the integral value of protons of the esterified substituents.

(2)-1 Elongation/strength evaluation The varnish was applied onto an 8-inch silicon wafer by spin coating using a coating and developing device ACT-8 so that the film thickness after pre-baking at 120°C for 3 minutes was 11 μm. After coating and prebaking, the temperature was raised to the curing temperature shown in Table 1 using an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.) at a rate of 3.5°C/min at an oxygen concentration of 20 ppm or less to cure. Heat treatment was carried out at the same temperature for 1 hour. When the temperature reached 50° C. or lower, the wafer was taken out, slowly cooled, and then immersed in 45% by mass hydrofluoric acid for 5 minutes to peel off the resin composition film from the wafer. This film was cut into strips with a width of 1 cm and a length of 3 cm. Using Tensilon RTM-100 (manufactured by Orientec Co., Ltd.), the film was pulled at a pulling speed of 5 mm/1 at a room temperature of 23.0°C and a humidity of 45.0% RH. The elongation at break and strength were measured. Measurements were performed on 10 strips per sample, and the average value of the top 5 points was determined from the results. Those with an elongation at break of 100% or more were evaluated as extremely good (A), those with an elongation of 50% or more but less than 100% were evaluated as good (B), and those with an elongation at break of less than 50% were evaluated as poor (D). Regarding the strength, a strength of 180 MPa or more and 350 MPa was classified as very good (A), a strength of 150 MPa or more and less than 180 MPa was classified as good (B), and a strength of less than 150 MPa was classified as poor (D).

(3) Pattern evaluation processing method (i)
The varnish was applied by spin coating onto an 8-inch silicon wafer on which a 100 nm copper sputtered film was formed using a coating and developing device ACT-8 (manufactured by Tokyo Electron Ltd.), and prebaked at 120°C for 3 minutes. Using an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.), the temperature was raised to the curing temperature shown in Table 1 at a rate of 3.5°C/min at an oxygen concentration of 20 ppm or less, and the temperature was maintained at the curing temperature for 1 hour. Heat treatment was performed. The obtained cured film with a thickness of 10 μm was heated using carbon dioxide laser (wavelength 1064 nm), YAG laser (wavelength 355 nm) which is UV laser, ArF excimer laser (wavelength 193 nm), KrF excimer laser (wavelength 248 nm), XeCl excimer laser (wavelength 308 nm). ) A via pattern was formed using 600 mJ/cm ² .

Processing method (ii)
For positive photosensitive resin compositions containing a photosensitizer such as a naphthoquinone diazide compound, the varnish is coated onto an 8-inch silicon wafer and spun using a developing device ACT-8 (manufactured by Tokyo Electron Ltd.). It was applied by a coating method to a film thickness of 10.5 μm to 12 μm, and prebaked at 120° C. for 3 minutes. A reticle with a circular via pattern cut thereon was set in an exposure machine i-line stepper DSW-8000 (manufactured by GCA), and exposed at an exposure dose of 1500 mJ/cm ² . After exposure, using the ACT-8 developing device, a 2.38% by mass tetramethylammonium aqueous solution (hereinafter referred to as TMAH, manufactured by Tama Chemical Industry Co., Ltd.) was discharged using the paddle method for 10 seconds. Development for 40 seconds was repeated twice, and then rinsed with pure water and shaken off to dry to obtain a pattern with a film thickness of 10 μm.

Processing method (iii)
For negative photosensitive resin compositions containing photosensitive agents such as polymerization initiators and photopolymerizable compounds, the varnish is applied onto an 8-inch silicon wafer using a developing device ACT-8 (manufactured by Tokyo Electron Ltd.). ) was applied by spin coating to a film thickness of 10.5 μm to 12 μm, and prebaked at 120° C. for 3 minutes. A reticle with a circular via pattern cut thereon was set in an exposure machine i-line stepper DSW-8000 (manufactured by GCA), and exposed at an exposure dose of 1500 mJ/cm ² . After exposure, using the ACT-8 developing device, repeat development twice using cyclopentanone using the paddle method with a developer discharge time of 10 seconds and a paddle time of 40 seconds, then rinse with pure water and shake off to dry. A pattern with a film thickness of 10 μm was obtained.
The patterns obtained by processing methods (i), (ii), and (iii) were observed using a scanning electron microscope (SEM, Hitachi High-Technologies S-3000N) at a magnification of 5000 times, and the via pattern was resolved without any residue. The minimum dimension of the image was defined as the resolution.

(4) Reliability evaluation in rewiring structure (FO-WLP similar structure evaluation)
After forming a temporary bonding material TP-300 (manufactured by Toray Industries, Inc.) on an 8-inch glass wafer as a supporting substrate, varnish was applied by spin coating using a spinner (manufactured by Mikasa Corporation), and then a hot plate was applied. (D-SPIN manufactured by Dainippon Screen Mfg. Co., Ltd.) at 120°C for 3 minutes, aiming for a via pattern opening of 50 μm, and processing using the same method as in (3) pattern evaluation to obtain a 10 μm thick A substrate on which a resin cured film (first layer cured film) was formed was obtained. Thereafter, a titanium target was placed in a sputtering device (SPL-500 manufactured by Nichiden Anelva), and the substrate was placed in a sample holder. A titanium layer was formed by mixing oxygen into argon gas (gas flow rate: 20 sccm of argon/3 sccm of oxygen) and sputtering to a film thickness of 100 nm. Furthermore, using the same apparatus, a copper layer was formed with a copper target to a thickness of 100 nm. After that, a resist of TMMR P-W1000 (manufactured by Tokyo Ohka Co., Ltd.) was applied, a 20 μm L/S pattern was formed, and electrolytic copper plating was performed so that the layer thickness was 4 μm. 120 (manufactured by Tokyo Ohka Co., Ltd.), and copper etching and Ti etching were performed using etching solutions WLC-C2 and WLC-T (manufactured by Mitsubishi Gas Chemical Co., Ltd.), respectively, to form a film of 10 μmL with a film thickness of 4 μm. /S (A copper pattern for first layer rewiring (first layer rewiring) was formed.

On this substrate, a cured resin film (second layer cured film) with a thickness of 10 μm was formed by processing in the same manner as described above except for aiming at a via pattern opening of 20 μm. Furthermore, a 10 μmL/S copper pattern (second layer rewiring) was formed using the same apparatus, resist, stripping solution, and etching solution as described above.

A cured resin film (third layer cured film) having a thickness of 10 μm was formed on this substrate by processing in the same manner as described above except for aiming at a via pattern opening of 5 μm. Furthermore, a 2 μmL/S copper pattern (third layer rewiring) was formed using the same apparatus, resist, stripping solution, and etching solution as described above.

A silicon chip with a thickness of 100 μm and a size of 10 mm*10 mm was placed above, and after forming a sealing resin, the glass substrate was peeled off to obtain a substrate with a similar structure to FO-WLP.

This substrate was subjected to 500 cycles of treatment (hereinafter referred to as -60°C⇔150°C) using a TC apparatus, with each cycle consisting of 15 minutes at 150°C. Each of the treated substrates was cut in cross section using an ion milling device (IM4000, manufactured by Hitachi High Technologies, Ltd.), and the cross section was observed using a scanning electron microscope (SEM, S-3000N, manufactured by Hitachi High Technologies, Ltd.). In each layer, a layer with a via pattern opening in the cured film, no cracks, no peeling of the cured film and copper wiring, and no cohesive peeling of copper wiring (peeling of the copper layer and copper oxide layer) is considered to be a pass. Those that passed the test for the first layer were evaluated as very good (A), those that passed the second layer were evaluated as better (B), and those that passed the first layer were evaluated as good (C). Applicable is a layer in which peeling (separation of the copper layer and copper oxide layer) occurs, but the cured film has via pattern openings and no cracks (D) is not acceptable (E) is a layer that fails in all layers. ).

(Synthesis example 1)
Synthesis of (A-0) Under a stream of dry nitrogen, p-phenylenediamine (10.81 g, 0.1 mol) was dissolved in N-methyl-2-pyrrolidone (NMP) in 400 g of NMP, and then pyromellitic dianhydride was dissolved. (21.81 g, 0.10 mol) was added and reacted at 40° C. for 2 hours. Thereafter, pyridine (0.79 g, 0.01 mol) was added and stirred at 60° C. for 2 hours. After the reaction was completed, the solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a polyimide precursor (A-0). The resin thus obtained had an imidization rate of 10% and an esterification rate of 0%. The weight average molecular weight was 62,300, and the PDI was 2.3.

(Synthesis example 2)
Synthesis of (A-1) Under a stream of dry nitrogen, 4,4'-diaminophenyl ether (DAE) (19.6 g, 0.098 mol), 1,3-bis(3-aminopropyl)tetramethyldisiloxane ( SiDA) (0.50 g, 0.002 mol) was dissolved in 400 g of N-methyl-2-pyrrolidone (NMP), and then 4,4'-oxydiphthalic dianhydride (31.0 g, 0.1 mol) was dissolved in 400 g of N-methyl-2-pyrrolidone (NMP). ) was added and reacted at 40°C for 2 hours. Then, pyridine (0.79 g, 0.01 mol) was added and stirred at 80° C. for 2 hours. After the reaction was completed, the solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a dryer at 50° C. for 72 hours to obtain a polyimide precursor polymer (A-1). The resin thus obtained had an imidization rate of 18% and an esterification rate of 0%. The weight average molecular weight was 50,600, and the PDI was 2.2.

(Synthesis example 3)
Synthesis of (A-1-2) Similar to (A-1), under a stream of dry nitrogen, 4,4'-diaminophenyl ether (DAE) (19.6 g, 0.098 mol), 1,3-bis( 3-Aminopropyl)tetramethyldisiloxane (SiDA) (0.50 g, 0.002 mol) was dissolved in 400 g of N-methyl-2-pyrrolidone (NMP), then 4,4'-oxydiphthalic dianhydride. (31.0 g, 0.1 mol) was added and reacted at 40°C for 2 hours. Then, pyridine (0.79 g, 0.01 mol) was added, stirred at 80°C for 2 hours, cooled to 40°C, and N,N-dimethylformamide dimethyl acetal (7.1 g, 0.005 mol) was added. A solution diluted with 10 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 40°C for 3 hours. After the reaction was completed, the solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. After the reaction was completed, the solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a dryer at 50° C. for 72 hours to obtain a polyimide precursor polymer (A-1-1). The resin thus obtained had an imidization rate of 18% and an esterification rate of 10%. The weight average molecular weight was 50,900, and the PDI was 2.1.

(Synthesis example 4)
Synthesis of (A-2) 4,4'-oxydiphthalic dianhydride (155.1 g, 0.5 mol) was placed in a 2-liter separable flask, and 125 g of 2-hydroxyethyl methacrylate and 400 ml of γ-butyrolactone were added. The mixture was stirred at room temperature, and 81.5 g of pyridine was added while stirring to obtain a reaction mixture. After the exotherm due to the reaction was completed, the mixture was allowed to cool to room temperature and left for 16 hours.

Next, under ice-cooling, a solution of 206.3 g of dicyclohexylcarbodiimide dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-diaminodiphenyl ether (95.0 g, A suspension of .48 mol) in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was dropped into 28 L of water to precipitate the polymer, and the resulting precipitate was filtered off and vacuum dried to obtain a powder of polyimide precursor (A-2). The imidization rate of the resin thus obtained was 14%, and the esterification rate with 2-ethyl methacrylate groups was 86%. The weight average molecular weight was 38,600, and the PDI was 2.1.

(Synthesis example 5)
Synthesis of (A-3) Under a stream of dry nitrogen, 4,4'-diaminophenyl ether (DAE) (19.6 g, 0.098 mol), 1,3-bis(3-aminopropyl)tetramethyldisiloxane ( N-methyl-2-pyrrolidone (NMP) (SiDA) (0.50 g, 0.002 mol) was dissolved in 400 g of NMP, and then 4,4'-oxydiphthalic dianhydride (31.0 g, 0.1 mol) was dissolved in 400 g of NMP. ) was added and reacted at 40°C for 2 hours.
Thereafter, a solution of N,N-dimethylformamide dimethyl acetal (35.8 g, 0.03 mol) diluted with 10 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 40°C for 3 hours. After the reaction was completed, the solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a polyimide precursor (A-3). The imidization rate of the resin thus obtained was 40%, and the esterification rate by methyl groups was 50%. The weight average molecular weight was 70,300, and the PDI was 2.2.

(Synthesis example 6)
Synthesis of (A-4) Under a stream of dry nitrogen, 4,4'-diaminophenyl ether (DAE) (19.6 g, 0.098 mol), 1,3-bis(3-aminopropyl)tetramethyldisiloxane ( N-methyl-2-pyrrolidone (NMP) (SiDA) (0.50 g, 0.002 mol) was dissolved in 400 g of NMP, and then 4,4'-oxydiphthalic dianhydride (31.0 g, 0.1 mol) was dissolved in 400 g of NMP. ) was added and reacted at 40°C for 2 hours.
Thereafter, a solution of N,N-dimethylformamide dimethyl acetal (35.8 g, 0.03 mol) diluted with 10 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 60°C for 3 hours. After the reaction was completed, the solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a polyimide precursor (A-4). The imidization rate of the resin thus obtained was 80%, and the esterification rate by methyl groups was 15%. The weight average molecular weight was 72,300, and the PDI was 2.1.

(Synthesis example 7)
Synthesis of (A-5) Under a stream of dry nitrogen, 4,4'-diaminophenyl ether (DAE) (20.0 g, 0.10 mol) and N-methyl-2-pyrrolidone (NMP) were dissolved in 400 g of NMP. Next, 4,4'-oxydiphthalic dianhydride (31.0 g, 0.1 mol) was added and reacted at 40° C. for 2 hours. Thereafter, a solution of N,N-dimethylformamide dimethyl acetal (23.8 g, 0.02 mol) diluted with 10 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 60°C for 3 hours. After the reaction was completed, the solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a polyimide precursor (A-5). The imidization rate of the resin thus obtained was 14%, and the esterification rate by methyl groups was 60%. The weight average molecular weight was 98,300, and the PDI was 2.3.

(Synthesis example 8)
Synthesis of (A-6) Under a stream of dry nitrogen, 4,4'-diaminophenyl ether (DAE) (3.0 g, 0.015 mol) and p-phenylenediamine (9.19 g, 0.085 mol) were -Methyl-2-pyrrolidone (NMP) was dissolved in 400 g of NMP, then 3,3',4,4'-biphenyltetracarboxylic dianhydride (29.42 g, 0.10 mol) was added and the mixture was heated at 40°C. The reaction was allowed to proceed for 2 hours. Thereafter, a solution of N,N-dimethylformamide dimethyl acetal (23.8 g, 0.02 mol) diluted with 10 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 60°C for 3 hours. After the reaction was completed, the solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a polyimide precursor (A-5). The imidization rate of the thus obtained resin was 18%, and the esterification rate by methyl groups was 70%. The weight average molecular weight was 98,300, and the PDI was 2.3.

(Synthesis example 9)
Synthesis of (A-7) Under a nitrogen stream, 27.2 g (0.4 mol) of imidazole was placed in a 250 ml three-necked flask, and 100 g of methylene chloride was added thereto, followed by stirring at room temperature. This was cooled to below -5°C, and a liquid obtained by dispersing 29.5 g (0.1 mol) of 4,4'-diphenyletherdicarboxylic acid dichloride in 100 g of methylene chloride was added to the reaction solution so that the temperature did not exceed 0°C. The mixture was added dropwise in this manner over an hour. After the dropwise addition, the reaction solution was further stirred at room temperature for 3 hours, and the precipitate generated during the reaction was filtered. The filtered precipitate was washed several times with pure water and dried in a vacuum oven at 50°C for 100 hours to obtain acid A.

Under a stream of dry nitrogen, BAHF (14.6 g, 0.040 mol) and RT-1000 (7.5 g, 0.0075 mol) were dissolved in 100 g of NMP. Acid A (6.76 g, 0.023 mol) was added thereto together with 10 g of NMP, and the mixture was reacted at 85° C. for 3 hours. Then, BAHF (1.0 g, 0.0025 mol), 1,3-bis(3-aminopropyl)tetramethyldisiloxane (0.62 g, 0.0025 mol), 5-norbornene-2,3-dicarboxylic acid (0.82 g, 0.005 mol) was added together with 5 g of NMP and reacted at 85°C for 1 hour, and then 4,4'-oxydiphthalic anhydride (6.93 g, 0.023 mol) was added together with 5 g of NMP at 85°C. The reaction was allowed to proceed for 1 hour. After the reaction was completed, the mixture was cooled to room temperature, acetic acid (13.20 g, 0.25 mol) was added together with 25 g of NMP, and the mixture was stirred at room temperature for 1 hour. After the stirring was completed, the solution was poured into 1.5 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a ventilation dryer at 50°C for three days to obtain powder (A-7). The resin thus obtained had an imidization rate of 82% and an esterification rate of 0%. The weight average molecular weight was 35,300, and the PDI was 1.9.

(Synthesis example 10)
Synthesis of (A-8) Under a stream of dry nitrogen, 4,4'-diaminophenyl ether (DAE) (19.6 g, 0.098 mol), 1,3-bis(3-aminopropyl)tetramethyldisiloxane ( SiDA) (0.50 g, 0.002 mol) was dissolved in 400 g of N-methyl-2-pyrrolidone (NMP), and then 4,4'-oxydiphthalic dianhydride (31.0 g, 0.1 mol) was dissolved in 400 g of N-methyl-2-pyrrolidone (NMP). ) was added and reacted at 40°C for 2 hours. Thereafter, the mixture was stirred at 80°C for 2 hours. After the reaction was completed, the solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a dryer at 50° C. for 72 hours to obtain a polyimide precursor polymer (A-8). The resin thus obtained had an imidization rate of 4% and an esterification rate of 0%. The weight average molecular weight was 40,600, and the PDI was 2.1.

(Synthesis example 11)
Synthesis of (A-9) Under a stream of dry nitrogen, 4,4'-diaminophenyl ether (DAE) (19.6 g, 0.098 mol), 1,3-bis(3-aminopropyl)tetramethyldisiloxane ( SiDA) (0.50 g, 0.002 mol) was dissolved in 400 g of N-methyl-2-pyrrolidone (NMP), and then 4,4'-oxydiphthalic dianhydride (31.0 g, 0.1 mol) was dissolved in 400 g of N-methyl-2-pyrrolidone (NMP). ) was added and reacted at 40°C for 2 hours. Thereafter, pyridine (0.79 g, 0.01 mol) was added and stirred at 180° C. for 2 hours. After the reaction was completed, the solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a dryer at 50° C. for 72 hours to obtain a polyimide precursor polymer (A-9). The resin thus obtained had an imidization rate of 90% and an esterification rate of 0%. The weight average molecular weight was 60,600, and the PDI was 2.1.

(Synthesis example 12)
Synthesis of (A-10) Under a stream of dry nitrogen, p-phenylenediamine (10.81 g, 0.1 mol) and N-methyl-2-pyrrolidone (NMP) were dissolved in 400 g of NMP, and then pyromellitic dianhydride was dissolved. (21.81 g, 0.10 mol) was added and reacted at 40° C. for 2 hours. Thereafter, the mixture was stirred at 80°C for 3 hours. After the reaction was completed, the solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a polyimide precursor (A-10). The resin thus obtained had an imidization rate of 3% and an esterification rate of 0%. The weight average molecular weight was 52,300, and the PDI was 2.3.
Each component used in Examples and Comparative Examples is shown below.

(Synthesis example 13)
Synthesis of (A-13) Under a stream of dry nitrogen, 4,4'-diaminophenyl ether (DAE) (3.0 g, 0.015 mol), 4,4'-diaminodicyclohexylmethane 15.15 g (17.88 g, N-methyl-2-pyrrolidone (NMP) was dissolved in 400 g of NMP, and then pyromellitic dianhydride (21.81 g, 0.10 mol) was added and reacted at 40°C for 2 hours. Ta. Thereafter, a solution of N,N-dimethylformamide dimethyl acetal (23.8 g, 0.02 mol) diluted with 10 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 60°C for 3 hours. After the reaction was completed, the solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a polyimide precursor (A-13). The imidization rate of the thus obtained resin was 19%, and the esterification rate by methyl groups was 51%. The weight average molecular weight was 68,300, and the PDI was 2.3.

(Synthesis example 14)
Synthesis of (A-14) Under a stream of dry nitrogen, 4,4'-diaminophenyl ether (DAE) (3.0 g, 0.015 mol), 4,4'-diaminodicyclohexylmethane (17.88 g, 0.085 mol) N-methyl-2-pyrrolidone (NMP) was dissolved in 400 g of NMP, and then 3,3',4,4'-biphenyltetracarboxylic dianhydride (29.42 g, 0.10 mol) was added. , and reacted at 40°C for 2 hours. Thereafter, a solution of N,N-dimethylformamide dimethyl acetal (23.8 g, 0.02 mol) diluted with 10 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 60°C for 3 hours. After the reaction was completed, the solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a polyimide precursor (A-14). The imidization rate of the resin thus obtained was 20%, and the esterification rate by methyl groups was 55%. The weight average molecular weight was 88,300, and the PDI was 2.3.

(Synthesis example 15)
Synthesis of (A-15) Under a stream of dry nitrogen, 4,4'-diaminophenyl ether (DAE) (6.0 g, 0.03 mol), 4,4'-diaminodicyclohexylmethane (14.72 g, 0.07 mol) N-methyl-2-pyrrolidone (NMP) was dissolved in 400 g of NMP, and then 3,3',4,4'-biphenyltetracarboxylic dianhydride (29.42 g, 0.10 mol) was added. , and reacted at 40°C for 2 hours. Thereafter, a solution of N,N-dimethylformamide dimethyl acetal (23.8 g, 0.02 mol) diluted with 10 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 60°C for 3 hours. After the reaction was completed, the solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a polyimide precursor (A-14). The imidization rate of the resin thus obtained was 38%, and the esterification rate by methyl groups was 45%. The weight average molecular weight was 91,200, and the PDI was 2.3.
(B-1) N-methylpyrrolidone (C-1) pyridine (pH=8.5)
(C-2) Imidazole (pH=9.8)
(C-3) Triethylamine (pH=12.3)
(C-4) 2-ethyl-4methylimidazole (pH=10.5)
(E-1): Polyflow 77 (manufactured by Kyoeisha Chemical Co., Ltd.)
[Examples 1 to 21, Comparative Example 1]
(a) As the resin, the above resins (A-0) to (A-6), (A-13) to (A-15) 10 g, (B-1) 20 g, (c) component 0.1 g, (d A varnish was prepared by blending 3.0 g of component () and 0.01 g of component (e) in the composition shown in Table 1.

[Comparative example 2]
(a) As resin, 10 g of the above resin (A-2), 20 g of (B-1), 2.0 g of photosensitizer (f-1), 2.0 g of (f-2), and antioxidant (f-3). )0.1g was blended to prepare a varnish of a negative photosensitive resin composition.

[Comparative example 3]
10 g of the above resin (A-7), 20 g of (B-1), 3.0 g of component (d), 2.0 g of naphthoquinone diazide photosensitizer (f-4), 0.1 g of antioxidant (f-3) A varnish of a positive photosensitive resin composition was prepared by blending the following.

[Comparative Examples 4 to 6]
Blending 10 g of the above resins (A-7) to (A-10), 20 g of (B-1), 0.1 g of component (c), 3.0 g of component (d), and 0.01 g of component (e), Varnish was made.

[Comparative Example 7]
20 g of bisphenol type epoxy resin ZX1059 (manufactured by Nippon Steel Chemical Co., Ltd.), 20 g of novolak type epoxy resin containing a xylene structure YX7700 (manufactured by Mitsubishi Chemical Corporation), and 3 g of phenoxy resin YL7553BH30 (manufactured by Mitsubishi Chemical Corporation) were mixed. The resin is (A-11), (B-1) 20 g, (C-1) 0.1 g, triazine skeleton-containing phenolic curing agent LA-7054 (manufactured by DIC Corporation) 6 parts, naphthalene type curing agent SN -485 (manufactured by Nippon Steel Chemical Co., Ltd.) 6 g, flame retardant HCA-HQ (manufactured by Sanko Co., Ltd. "HCA-HQ" 2 g, phenylaminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") ) and 110 parts of spherical silica SOC1 ("SOC1" manufactured by Admatex Co., Ltd.) were mixed and uniformly dispersed with a high-speed rotating mixer to prepare a varnish.
[Comparative example 8]
5 g of the above resin (A-10), 5 g of polytetrafluoroethylene resin powder KTL-8N (A-12) (manufactured by Kitamura Co., Ltd.), 20 g of (B-1), and 0.1 g of component (c) were added in Table 1. A varnish was obtained by blending the composition shown in .

Table 1 shows the composition and curing temperature of the resin compositions obtained in each Example and Comparative Example.

Table 2 shows the characteristics and processing methods of the resin compositions obtained in each Example and Comparative Example.

Comparing Examples 1 to 21 and Comparative Examples 1 to 8, Examples 1 to 21 have an imidization rate of 5% or more and less than 90%, and the resolution and reliability evaluation results are improved by using a UV laser. are doing.

Comparing Examples 2 to 21 and Example 1, in Examples 2 to 21, the tensile elongation of the cured film obtained by curing the resin composition was 50% or more, the tensile strength was 150 to 450 MPa, and the UV laser was not applied. By using this method, both resolution and reliability evaluation results are improved.

Comparing Examples 3 to 6 with Examples 1 and 2, Examples 3 to 6 contain (c) a basic additive, and the resolution and reliability evaluation results are improved.

Comparing Examples 7 to 13, 19 to 21 and Examples 1 to 6, it is found that in Examples 7 to 13, 19 to 21, (a) the resin contains a carboxylic acid residue, and the resin contains an ester of the carboxylic acid residue. The conversion rate is 10% or more and less than 90%, and the resolution result is improved.

Comparing Examples 8 to 13, 19 to 21 and Example 7, in Examples 8 to 13 and 19 to 21, (a) the esterified substituent of the carboxylic acid residue in the resin is an alkyl group with a molecular weight of 100 or less or/and alkyl ether groups, resulting in improved resolution.

Comparing Examples 8 to 9, 13, and 21 with Examples 10 to 12, Examples 8 to 9, and 13 have diamine residues and carboxylic acid residues containing the structure represented by the general formula (1). The combined ratio of residues is 10 to 99 mol%, and the resolution results are improved.

Comparing Examples 19 and 20 and Example 11, in Examples 20 and 21, the resin (a) has an alicyclic diamine residue, and two or more benzene rings are bonded by a single bond. The alicyclic diamine residue has one or more structures selected from the group consisting of general formula (2), general formula (3), and general formula (4). , with improved strength and resolution results.

Comparing Examples 5 to 6 and Examples 3 to 4, in Examples 5 to 6, the basic additive (c) was an additive with a pH of 9.5 to 11.5, and the resolution results were improved. There is.

Comparing Example 5 with Examples 1 to 4, in Example 5, the basic additive (c) is an imidazole derivative having two or more substituents, and the resolution results are improved.

Comparing Example 13 with Examples 8 to 12, Example 13 is a resin having a polyimide precursor structure with an imidization rate of 20% or more and less than 70%, has improved elongation and strength, and has improved resolution and Both reliability evaluation results have been improved.

Comparing Examples 14 to 15 with Example 13, Examples 14 to 15 contain (d) a crosslinking agent and have improved resolution results.

Comparing Example 15 and Example 14, Example 15 contains (e) a surfactant and has improved resolution results.

Comparing Example 11, Examples 16 to 18, and Example 18, in Example 11 and Examples 16 to 18, the UV laser is an excimer laser, and the resolution results are improved.

Comparing Example 11 with Examples 16 to 18, in Example 11, the UV laser is a KrF excimer laser, and the resolution results are improved.

Comparing Example 11 and Example 12, Example 11 includes a step of heat treatment at 180° C. or lower and a step of ablation processing with a UV laser, and has improved resolution.

(D-1), (f-1), (f-2), (f-3), and (f-4) are compounds shown in the following chemical formulas, respectively.

1 Silicon wafer 2 Al pad 3 Passivation film 4 Insulating film 5 Metal (Cr, Ti, etc.) film 6 Metal wiring (Al, Cu, etc.)
7 Insulating film 8 Barrier metal 9 Scribe line 10 Solder bump 11 Sealing resin 12 Substrate 13 Insulating film 14 Insulating film 15 Metal (Cr, Ti, etc.) film 16 Metal wiring (Ag, Cu, etc.)
17 Metal wiring (Ag, Cu, etc.)
18 Electrode 19 Sealing resin 20 Support substrate (glass substrate, silicon wafer)
21 Electrode pad (Cu)
22 Insulating film 23 Metal wiring (Cu)
24 Cu post 25 Solder bump 26 Semiconductor chip 27 TFT (thin film transistor)
28 Wiring 29 TFT insulating layer 30 Flattening layer 31 ITO (transparent electrode)
32 Substrate 33 Contact hole 34 Insulating layer

Claims (21)

A resin composition containing (a) a resin, (b) a solvent,
The resin (a) is a resin having a polyimide precursor structure with an imidization rate of 5% or more and less than 90%, and the resin (a) is a diamine residue containing a structure represented by general formula (1). a diamine residue containing a structure represented by general formula (1), with the total of all carboxylic acid residues and all amine residues contained in the resin (a) being 100 mol%; The proportion of residues including carboxylic acid residues is 10 to 99 mol%, and the diamine residue containing the structure represented by the general formula (1) is bis(3,3,4'- Any of diaminodiphenyl ether residue, 4,4'-diaminodiphenyl ether residue, bis{4-(4-aminophenoxy)phenyl}ether residue, and 1,4-bis(4-aminophenoxy)benzene residue A resin composition for ablation processing using a UV laser.

(In the general formula (1), R represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. a and b are integers of 0 to 4. * mark represents a bonding part.) A resin composition containing (a) a resin, (b) a solvent,
The resin (a) is a resin having a polyimide precursor structure with an imidization rate of 5% or more and less than 90%, and is the sum of all carboxylic acid residues and all amine residues contained in the resin (a). Ablation using a UV laser in which the total proportion of diamine residues and carboxylic acid residues containing the structure represented by general formula (1) is 60 to 99 mol%, with the total amount being 100 mol%. Resin composition for processing.

(In the general formula (1), R represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. a and b are integers of 0 to 4. * mark represents a bonding part.) The resin composition according to claim 1 or 2, wherein a cured film obtained by curing the resin composition has a tensile elongation of 50% or more and a tensile strength of 150 to 450 MPa. The resin composition according to any one of claims 1 to 3, further comprising (c) a basic additive. The resin composition according to any one of claims 1 to 4, wherein the resin (a) contains a carboxylic acid residue, and the esterification rate of the carboxylic acid residue is 10% or more and less than 90%. 6. The resin composition according to claim 5, wherein the esterified substituent of the carboxylic acid residue in the resin (a) is an alkyl group and/or an alkyl ether group having a molecular weight of 100 or less. The resin (a) has an alicyclic diamine residue and a carboxylic acid residue structure in which two or more benzene rings are bonded with a single bond,
Any one of claims 1 to 6, wherein the alicyclic diamine residue has one or more structures selected from the group consisting of general formula (2), general formula (3), and general formula (4). The resin composition according to claim 1.

(In general formula (2), the * mark represents a bonding part.)

(In general formula (3), R ¹ and R ² may be the same or different, and each represents a hydrogen atom, a methyl group, or a trifluoromethyl group. In addition, m represents an integer within the range of 1 to 10. (In addition, the asterisk (*) represents the joint.)

(In general formula (4), R ³ and R ⁴ may be the same or different, and each represents a hydrogen atom, a methyl group, or a trifluoromethyl group. Also, the mark * represents a bonding part.) The basic additive (c) is an additive having a pH of 9.5 to 11.5, and the content of the basic additive (c) to 100 parts by mass of the (a) resin is 0.1 parts by mass to 10 parts by mass. 7. The resin composition according to claim 3, wherein the resin composition is The resin composition according to any one of claims 3 to 8, wherein the basic additive (c) is an imidazole derivative having two or more substituents. The resin composition according to any one of claims 1 to 9, wherein the resin (a) is a resin having a polyimide precursor structure with an imidization rate of 20% or more and less than 70%. The resin composition according to any one of claims 1 to 10, further comprising (d) a crosslinking agent, wherein the (d) crosslinking agent has three or more methylol groups or alkoxymethyl groups. The resin composition according to any one of claims 1 to 11, further comprising (e) a surfactant, wherein the (e) surfactant is an acrylic polymer. A cured film obtained by curing the resin composition according to any one of claims 1 to 12 and ablated with a UV laser. The cured film according to claim 13, wherein the UV laser is an excimer laser. The cured film according to claim 14, wherein the UV laser is a KrF excimer laser. Production of a relief pattern of a cured film, comprising a step of applying the resin composition according to any one of claims 1 to 12 on a substrate, a step of heat treatment at 180° C. or less, and a step of ablation processing with a UV laser. Method. An electronic component or a semiconductor device, wherein the cured film according to any one of claims 13 to 15 is disposed as an interlayer insulating film between rewirings. 18. The electronic component or semiconductor device according to claim 17, wherein the rewiring is a copper metal wiring, and the width of the copper metal wiring and the interval between adjacent wirings are 5 μm or less. The electronic component according to claim 17 or 18, wherein the cured film according to any one of claims 13 to 15 is arranged as an interlayer insulating film between rewirings on a sealing resin substrate on which a silicon chip is arranged. or semiconductor devices. The electronic component or semiconductor device according to any one of claims 17 to 19, wherein the width of the metal wiring and the interval between adjacent wirings become narrower as the rewiring layer according to claim 17 approaches the semiconductor chip. arranging the cured film according to any one of claims 13 to 15 as an interlayer insulating film between rewirings on the support substrate on which the temporary pasting material is arranged;
A step of placing a silicon chip and a sealing resin thereon;
After that, it includes a step of peeling off the support substrate on which the temporary pasting material is placed and the rewiring.
A method for manufacturing electronic components or semiconductor devices.

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