JP2018173573A - Photosensitive resin composition, method for producing pattern cured product, cured product, interlayer insulation film, cover coat layer, surface protective film, and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having excellent mechanical characteristics and photosensitive properties, and a method for producing a pattern cured product, a cured product, an interlayer insulation film, a cover coat layer, a surface protective film, and an electronic component, using the same.SOLUTION: A photosensitive resin composition contains (a) a polymer having an acidic functional group or its inductive substituent, (b) a crosslinker, (c) a photosensitizer, and (d) a silane coupling agent having one or more functional groups, the functional groups being one or more selected from the group consisting of a methyl group, a phenyl group, an epoxy group, a mercapto group, an amino group, an isocyanate group, a vinyl group, an acryloyl group, a methacryloyl group and an allyl group.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition, a method for producing a patterned cured product, a cured product, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component.

In recent years, photosensitive resin compositions in which photosensitive properties are imparted to polyimide and polybenzoxazole, which have excellent heat resistance, electrical properties, mechanical properties, etc., have been used for surface protective films and interlayer insulating films of semiconductor elements. Yes.
Moreover, the photosensitive resin composition which can be developed with alkaline aqueous solution is proposed (for example, refer patent document 1 and 2).

In recent years, a stacked device structure has attracted attention for higher performance and higher speed (for example, Non-Patent Document 1).
In the production of a laminated device structure, rewiring is performed after sealing a diced chip. However, since the heat resistance of the sealing material is poor, an interlayer insulating film for rewiring that can be cured at low temperature is required.

JP 2009-265520 A International Publication No. 2014/115233

“Semiconductor Technology Yearbook 2013 Packaging / Mounting”, Nikkei BP Co., Ltd., December 2012, p. 41-50

  As a result of intensive studies on the low-temperature curable photosensitive resin composition by the present inventors, the resin is entangled with the photosensitive resin composition by mixing a crosslinking agent and a specific silane coupling agent. The present inventors have found a mechanism that the mechanical properties of the film are maintained in order to form a crosslinked structure apparently, thereby completing the present invention.

  An object of the present invention is to provide a photosensitive resin composition having excellent mechanical properties and photosensitive properties, a method for producing a patterned cured product using the same, a cured product, an interlayer insulating film, a cover coat layer, a surface protective film, and an electron To provide parts.

According to the present invention, the following photosensitive resin composition and the like are provided.
1. (A) a polymer having an acidic functional group or a derivative substituent thereof;
(B) a crosslinking agent;
(C) a photosensitizer;
(D) having one or more functional groups, wherein the functional group is composed of a methyl group, a phenyl group, an epoxy group, a mercapto group, an amino group, an isocyanate group, a vinyl group, an acryloyl group, a methacryloyl group, and an allyl group. The photosensitive resin composition containing the silane coupling agent which is 1 or more selected.
2. 2. The photosensitive resin composition according to 1, wherein the component (a) is at least one selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a copolymer thereof.
3. 3. The photosensitive resin composition according to 1 or 2, wherein the component (a) has a structural unit represented by the following formula (1).
(In Formula (1), U is a divalent organic group, a single bond, —O— or —SO ₂ —, and V is a divalent organic group.)
4). The photosensitive resin composition in any one of 1-3 whose weight average molecular weights of the said (d) component are 150 or more.
5. The photosensitive resin composition in any one of 1-4 whose content of the said (d) component is 1 mass part or more with respect to 100 mass parts of said (a) component.
A step of applying the photosensitive resin composition according to any one of 6.1 to 5 onto a substrate and drying to form a photosensitive resin film;
Forming a resin film by pattern exposure of the photosensitive resin film;
Developing the resin film after the pattern exposure using an alkaline aqueous solution, and forming a pattern resin film;
And a step of heat-treating the pattern resin film to form a pattern cured product.
A cured product obtained by curing the photosensitive resin composition according to any one of 7.1 to 5.
An interlayer insulating film, a cover coat layer or a surface protective film produced using the cured product according to 8.7.
An electronic component comprising the interlayer insulating film, cover coat layer or surface protective film according to 9.8.

  According to the present invention, a photosensitive resin composition having excellent mechanical properties and photosensitive properties, a method for producing a patterned cured product, a cured product, an interlayer insulating film, a cover coat layer, a surface protective film, and an electron using the same Parts can be provided.

It is one manufacturing process figure of the electronic component which concerns on one Embodiment of this invention. It is one manufacturing process figure of the electronic component which concerns on one Embodiment of this invention. It is one manufacturing process figure of the electronic component which concerns on one Embodiment of this invention. It is one manufacturing process figure of the electronic component which concerns on one Embodiment of this invention. It is one manufacturing process figure of the electronic component which concerns on one Embodiment of this invention. It is one manufacturing process figure of the electronic component which concerns on one Embodiment of this invention. It is one manufacturing process figure of the electronic component which concerns on one Embodiment of this invention. It is a schematic sectional drawing of the electronic component which concerns on one Embodiment of this invention.

Hereinafter, a photosensitive resin composition of the present invention, a method for producing a cured pattern, a cured product, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component using the same will be described in detail. . The present invention is not limited to the following embodiments.
In this specification, “A or B” may include either one of A and B, or may include both. In addition, in this specification, the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, the term “process” is used as long as the intended action of the process is achieved. included.
The numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In addition, in the present specification, the content of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity. Further, the exemplary materials may be used singly or in combination of two or more unless otherwise specified.

  As used herein, “(meth) acryloyl” means “acryloyl” and “methacryloyl”. Similarly, “(meth) acrylate” means “acrylate” and its corresponding “methacrylate”.

  The photosensitive resin composition of the present invention comprises (a) a polymer having an acidic functional group or a derivative substituent thereof (hereinafter also referred to as “(a) component”), and (b) a crosslinking agent (hereinafter referred to as “( b) component "), (c) photosensitizer (hereinafter also referred to as" component (c) "), and (d) one or more functional groups, wherein the functional group is a methyl group, A silane coupling agent that is at least one selected from the group consisting of phenyl group, epoxy group, mercapto group, amino group, isocyanate group, vinyl group, acryloyl group, methacryloyl group, and allyl group (hereinafter referred to as “component (d)”) Also).

  Thereby, the outstanding photosensitive characteristic can be shown and the hardened | cured material which has the outstanding mechanical characteristic can be obtained. In particular, it is possible to obtain a cured product exhibiting excellent elongation even after the pressure cooker test (PCT test).

  The photosensitive resin composition of the present invention is preferably a positive photosensitive resin composition.

  (A) As an acidic functional group of a component, a carboxy group, a phenolic hydroxyl group, etc. are mentioned.

The acidic functional group-derived substituent is preferably a group in which the hydrogen atom of the acidic functional group is a monovalent organic group.
Examples of the monovalent organic group of the derived substituent include an alkyl group (preferably having 1 to 20 carbon atoms), an aryl group (preferably having 6 to 20 ring carbon atoms), and a cycloalkyl group (preferably having 5 to 5 ring carbon atoms). 20), a hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 15 carbon atoms) such as an aralkyl group (preferably 6 to 20 carbon atoms), an alkoxyalkyl group (preferably 2 to 20 carbon atoms), an aryloxyalkyl group (Preferably having 7 to 20 carbon atoms), heterocyclic groups (preferably having 5 to 20 ring atoms), silyl groups, oxocycloalkyl groups (preferably having 5 to 20 ring atoms), and the like. It may have a substituent (hereinafter also referred to as “optional substituent”).

Examples of the optional substituent include an alkyl group having 1 to 6 carbon atoms (for example, a methyl group), an alkoxy group having 1 to 6 carbon atoms (for example, a methoxy group), an alkylthio group having 1 to 6 carbon atoms (for example, a methylthio group), nitro Group, a halogen atom such as a fluorine atom, a benzoxy group, a hydroxyl group, a trimethylsilyl group, an aryl group having 6 to 15 carbon atoms (for example, a phenyl group), and the like.
Arbitrary arbitrary substituents may combine to form a ring. Examples of the ring to be formed include a benzene ring and a cyclohexyl ring.

  The monovalent organic group of the derived substituent may include a hetero atom such as oxygen, sulfur, nitrogen and silicon or an organic group such as a ketone group, an ester group and an amide group in the skeleton.

  Specific examples of the monovalent organic group of the derived substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group, a cyclopropenyl group, and a cyclobutyl group. , Cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexenyl group, norbornyl group, norbornenyl group, adamantyl group, benzyl group, p-nitrobenzyl group, trifluoromethyl group, methoxyethyl group, ethoxyethyl group, methoxymethyl group, Ethoxymethyl group, methoxyethoxymethyl group, benzoxymethyl group, tetrahydropyranyl group, ethoxytetrahydropyranyl group, tetrahydrofuranyl group, 2-trimethylsilylethoxymethyl group, trimethylsilyl group, t-butyldimethylsilyl group, 3-oxocyclohexyl Group 9 Fluorenylmethyl group, methylthiomethyl group, a phenyl group, and the like. It is not limited to those listed.

  In addition, the monovalent organic group of the derived substituent may be a residue such as hydroxyalkyl (preferably alkyl having 1 to 6 carbon atoms) (meth) acrylate such as 2-hydroxyethyl methacrylate.

  The component (a) is not particularly limited as long as it is a polymer having an acidic functional group or a derivative substituent thereof, but is selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a copolymer thereof. The above is preferable. Among these, a polybenzoxazole precursor is more preferable.

The component (a) preferably has a structural unit represented by the following formula (1). Moreover, it is preferable that a polybenzoxazole precursor contains the structural unit represented by following formula (1).
Thereby, when i line | wire is used for pattern exposure, it is easy to make a transmittance | permeability high.

(In Formula (1), U is a divalent organic group, a single bond, —O— or —SO ₂ —, and V is a divalent organic group.)

The divalent organic group represented by U in the formula (1) is preferably a divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms (preferably 2 to 20 carbon atoms). The divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms is preferably linear or branched, and more preferably branched.
Said C1-C30 bivalent aliphatic hydrocarbon group may be substituted by the substituent, and a halogen atom (for example, fluorine atom) etc. are mentioned as a substituent.

The divalent organic group of U in the formula (1) is preferably a group represented by the following formula (UV1).
In formula (UV1), R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms (preferably 1, 2 or 3), or 1 to 6 carbon atoms (preferably 1 , 2 or 3), and a is an integer of 1 to 30.

Examples of R ¹ and R ² include a methyl group and a trifluoromethyl group, and a trifluoromethyl group is preferable from the viewpoint of transparency.
a is preferably an integer of 1 to 5.

  The polybenzoxazole precursor can be generally synthesized using a dicarboxylic acid or a derivative thereof and a dihydroxydiamine compound. V is preferably a dicarboxylic acid residue.

Examples of the divalent organic group represented by V in the formula (1) include a linear, branched or cyclic divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group.
In addition, the divalent organic group represented by V in the formula (1) includes two divalent aromatic hydrocarbon groups, a single atom, a heteroatom such as oxygen, sulfur, nitrogen and silicon, or the above formula (UV1). Or a divalent group bonded by an organic group such as a ketone group, an ester group or an amide group.
The divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group may have a substituent on the main chain. Examples of the substituent include the same as the optional substituent of the above-described derived substituent.

  Straight chain (preferably having 1 to 30 carbon atoms, more preferably 1 to 20, more preferably 7 to 20), branched chain (preferably having 2 to 30 carbon atoms, more preferably 2 to 20) or cyclic (preferably carbon The divalent aliphatic hydrocarbon group having a number of 3 to 30, more preferably 3 to 20 is, for example, an alkylene group (for example, a decylene group or a dodecylene group), a cyclopentylene group, a cyclohexylene group, or a cyclooctylene group. And a divalent bicyclo ring.

  Moreover, as said divalent aromatic hydrocarbon group (preferably C6-C30), a phenylene group, a naphthylene group, etc. are mentioned, for example.

Examples of the dicarboxylic acid include aliphatic dicarboxylic acids such as dodecanedioic acid and decanedioic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2 -Bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid, 4,4'-diphenyl ether dicarboxylic acid and the like are mentioned, and V corresponds to a group obtained by removing two carboxy groups from these.
Dicarboxylic acid may be used individually by 1 type, and may combine 2 or more types.

  The polybenzoxazole precursor of component (a) may have a structural unit other than the structural unit represented by formula (1). The proportion of the structural unit represented by the formula (1) is preferably 50 mol% or more, more preferably 60 mol% or more in all the structural units.

Since the polybenzoxazole precursor is usually developed with an aqueous alkaline solution, it is preferably soluble in the aqueous alkaline solution.
Examples of the alkaline aqueous solution include an organic ammonium aqueous solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution, a metal hydroxide aqueous solution, and an organic amine aqueous solution.
In general, it is preferable to use a TMAH aqueous solution having a concentration of 2.38% by mass.

  A polyimide precursor is a precursor which can be obtained by making tetracarboxylic dianhydride and a diamine compound react, for example.

  The polyimide precursor is a polyamic acid or an esterified product thereof, and those generally used for photosensitive resin compositions can be mentioned.

  Examples of the copolymer of the polyimide precursor and the polybenzoxazole precursor include the above-described copolymer of the polyimide precursor and the polybenzoxazole precursor. It may be a block copolymer or a random copolymer.

The component (a) is preferably soluble in the TMAH aqueous solution.
One criterion that the component (a) is soluble in an alkaline aqueous solution will be described below, for example. The component (a) is dissolved in an arbitrary solvent to form a solution, and then spin-coated on a substrate such as a silicon wafer to form a resin film having a thickness of about 5 μm. This is immersed in any one of tetramethylammonium hydroxide aqueous solution, metal hydroxide aqueous solution, and organic amine aqueous solution at 20 to 25 ° C. As a result, when dissolved into a solution, it is determined that the component (a) used is soluble in an alkaline aqueous solution.

The component (a) preferably has a weight average molecular weight of 10,000 to 100,000, more preferably 15,000 to 100,000, and still more preferably 20,000 to 85,000.
In the case of the said range, the solubility to a suitable alkali developing solution can be maintained and the viscosity of the photosensitive resin composition can be made appropriate.
The weight average molecular weight can be measured, for example, by gel permeation chromatography, and can be determined by conversion using a standard polystyrene calibration curve.
The dispersity obtained by dividing the weight average molecular weight by the number average molecular weight is preferably 1.0 to 4.0, more preferably 1.0 to 3.0.

  Examples of the component (b) include compounds represented by the following formula (2) or (3).

In formula (2), R ¹¹ is each independently a hydrogen atom or a group represented by —CH ₂ —O—R ¹² . At least one (preferably all) of R ¹¹ is a group represented by —CH ₂ —O—R ¹² . R ¹² is a hydrogen atom or an alkyl group having 1 to 6 carbon ^atoms, when ^{R 12} is ^{plural, R 12} may be the same or different.

In formula (3), each R ¹³ is independently a hydrogen atom or a monovalent organic group (preferably an alkyl group having 1 to 6 carbon atoms). R ¹⁴ is each independently a hydrogen atom or a monovalent organic group (preferably an alkyl group having 1 to 6 carbon atoms), and may be bonded to each other to form a ring structure that may have a substituent. Good. )

  Examples of the substituent of the ring structure include the same substituents as those of the above-mentioned derived substituent.

As a compound represented by Formula (3), the compound represented by following formula (10) is mentioned as a preferable thing.
(Wherein, Z is each independently represent an alkyl group having 1 to 6 carbon ^{atoms, R 15} represents an alkyl group having 1 to 6 carbon atoms independently.)

Regarding R ¹² to R ¹⁵ and Z, examples of the alkyl group having 1 to 6 carbon atoms (preferably 1, 2 or 3) include a methyl group, an ethyl group, and a butyl group.

  (B) A component may be used individually by 1 type and may combine 2 or more types.

  As for content of (b) component, 5 mass parts or more are preferable with respect to 100 mass parts of (a) component, 5-40 mass parts is more preferable, and 10-30 mass parts is more preferable.

Component (c) is, for example, a compound that generates an acid upon irradiation with actinic rays, and has a function of increasing the solubility of the irradiated portion in an alkaline aqueous solution.
Examples of actinic rays include ultraviolet rays such as i-rays, visible rays, and radiation.

Examples of the component (c) include diazonaphthoquinone compounds, aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts and the like. Among them, diazonaphthoquinone compounds are preferable because of their high sensitivity.
A diazonaphthoquinone compound is a compound having a diazonaphthoquinone structure.

  The diazonaphthoquinone compound can be obtained, for example, by subjecting o-quinonediazide sulfonyl chlorides to a hydroxy compound, an amino compound or the like (preferably a hydroxy compound) in the presence of a dehydrochlorinating agent.

  Examples of o-quinonediazidosulfonyl chlorides include 1,2-benzoquinone-2-diazide-4-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, and 1,2-naphthoquinone-2-diazide. -4-sulfonyl chloride and the like can be used.

  Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4,3 ', 4', 5'-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro- 1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2,1- ] Indene, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, and 1,1-bis (4-hydroxyphenyl) -1-{[2- (4-hydroxyphenyl) -2-propyl Phenyl} ethane or the like can be used.

  Examples of amino compounds include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl sulfide. , O-aminophenol, m-aminophenol, p-aminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3- Amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis ( 3-amino-4-hydroxyphenyl) hexafluo Propane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane and the like can be used.

  The content of the component (c) is preferably 0.01 to 50 parts by mass, and 0.1 to 30 parts by mass with respect to 100 parts by mass of the component (a) from the viewpoints of sensitivity and resolution during exposure. Is more preferable, 0.5-25 mass parts is further more preferable, and 3-20 mass parts is especially preferable.

The component (d) has 1 or more (preferably 2 or more, more preferably 5 or more, still more preferably 5 to 10) functional groups.
The functional group of component (d) is methyl group, phenyl group, epoxy group, mercapto group, amino group, isocyanate group, vinyl group, acryloyl group, methacryloyl group and allyl group (preferably epoxy group, mercapto group, amino group) , An isocyanate group, a vinyl group, an acryloyl group, a methacryloyl group, and an allyl group, more preferably an epoxy group, a mercapto group, an amino group, an acryloyl group, and a methacryloyl group.

(D) The weight average molecular weight of a component is 150 or more, 800-30,000 are preferable and 800-10,000 are more preferable.
(D) The number average molecular weight of a component is 150 or more, 800-30,000 are preferable and 800-10,000 are more preferable.
When the weight average molecular weight or number average molecular weight is 150 or more, the adhesion can be improved.
The weight average molecular weight can be measured, for example, by gel permeation chromatography, and can be determined by conversion using a standard polystyrene calibration curve.
The number average molecular weight can be determined by a known method. For example, the number average molecular weight may be calculated from the structure of the molecule obtained by NMR and the condensation number, or may be determined from liquid chromatography mass spectrometry, or a combination thereof. You may ask for it.
The dispersity obtained by dividing the weight average molecular weight by the number average molecular weight is preferably 1.0 to 4.0, more preferably 1.0 to 3.0.

(D) It is preferable that the viscosity (25 degreeC) of a component is 10-3000 mm < ² > / s.
The viscosity of component (d) can be measured by using, for example, an Ubbelohde viscometer, a rotational viscometer, or the like.

  The functional group equivalent of the component (d) (the mass of the resin containing 1 equivalent of the functional group) is preferably 100 to 1000 g / mol, and more preferably 200 to 850 g / mol.

  Epoxy equivalent (mass of resin containing 1 equivalent of epoxy groups) can be determined, for example, according to JIS K7236: 2009.

  The acrylic equivalent (mass of resin containing 1 equivalent of acryloyl group) can be calculated and calculated from, for example, (total charged monomer mass (g) + initiator mass (g)) / acrylate amount (mol).

Mercapto equivalent (mass of resin containing 1 equivalent of mercapto group) can be determined as follows, for example.
0.2 g of a sample is precisely weighed, and 20 mL of chloroform is added thereto to obtain a sample solution. Using a starch indicator dissolved in 0.275 g of soluble starch in 30 g of pure water, add 20 mL of pure water, 10 mL of isopropyl alcohol, and 1 mL of the starch indicator, and stir with a stirrer. Iodine solution (manufactured by Wako Pure Chemical Industries, Ltd., 0.05 mol / L iodine solution, factor: 1.003 (20 ° C.)) is dropped, and the end point is the point where the chloroform layer is green. From the above measurement, (sample mass (g) × 10000) / (titration amount of iodine solution (ml) × factor of iodine solution) can be calculated to obtain the mercapto equivalent.

Methacryl equivalent (mass of resin containing 1 equivalent of methacryloyl group) can be calculated | required similarly to an acrylic equivalent, for example.
The amino equivalent (the mass of the resin containing 1 equivalent of an amino group) can be determined, for example, by calculating the amine value by neutralization titration.

The component (d) preferably has an alkoxy group or a hydroxyl group. (D) It is preferable that the amount of alkoxy groups of a component is 10-70 mass%.
The amount of alkoxy groups can be measured by, for example, NMR.

The structural unit of the component (d) is a siloxane group or —Si (OR ²² ) _3-n (R ²³ ) _n (where R ²² , R ^23, and n are R ²² , R ^{23 in the following} formula (4)). And n as defined by n).

  Examples of the component (d) include a compound containing a structural unit represented by the following formula (4), a compound containing a structural unit represented by the formula (5), and a terminal group containing a silicon atom, and a formula (6) The compound containing the structural unit represented by these is mentioned.

In the formulas (4) and (5), R ²¹ represents a methyl group, a phenyl group, an epoxy group, a mercapto group, an amino group, an isocyanate group, a vinyl group, an acryloyl group, a methacryloyl group or an allyl group. R ²² and R ²³ each independently represents an alkyl group having 1 to 4 carbon atoms (preferably a methyl group). n represents 0, 1, 2 or 3.
When R ²² and R ²³ are 2 or more, each of the 2 or more R ²² and R ²³ may be the same or different.
R ²⁴ and R ²⁵ each independently represent a hydrogen atom, an alkyl group, an allyl group, an aryl group, an epoxy group, an oxetanyl group, a mercapto group, a (meth) acryloyl group, a vinyl group, an isocyanate group, or an amino group; ^At least one of ²⁴ and R ²⁵ represents a methyl group, a phenyl group, an allyl group, an epoxy group, a mercapto group, a (meth) acryloyl group, a vinyl group, an isocyanate group, or an amino group. L ¹ and L ² each independently represent a single bond or a linking group having 1 to 6 atoms in the linking portion.

The alkyl group of R ²⁴ and ^{R 25} (preferably having 1 to 20 carbon atoms), and the like methyl group.
Examples of the aryl group of R ²⁴ and R ²⁵ (preferably having 6 to 20 ring carbon atoms) include a phenyl group.
Examples of the linking group having 1 to 6 atoms in the linking part of L ¹ and L ² include —O—CH ₂ —.

  It is preferable that the terminal group of the compound which contains the structural unit represented by Formula (5), and a terminal group contains a silicon atom contains group represented by Formula (5A).

(In formula (5A), each R ²⁶ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (preferably a methyl group or an ethyl group). R ²⁷ each independently has 1 to 4 carbon atoms. Represents an alkyl group (preferably a methyl group or an ethyl group; m represents 0, 1, 2 or 3)

When R ²⁶ and R ²⁷ are 2 or more, each of the 2 or more R ²⁶ and R ²⁷ may be the same or different.

In formula (6), R ²⁸ represents an alkoxy group having 1 to 4 carbon atoms (preferably a methoxy group or ethoxy group) or an alkyl group having 1 to 4 carbon atoms (preferably a methyl group or an ethyl group). X represents a methyl group, phenyl group, allyl group, epoxy group, mercapto group, (meth) acryloyl group, vinyl group, isocyanate group or amino group. L ³ represents a single bond or an alkylene group having 1 to 6 carbon atoms (preferably a methylene group, an ethylene group or a propylene group).

  The component (d) may include a structural unit other than the structural unit represented by the formula (4), the structural unit represented by the formula (5), and the structural unit represented by the formula (6).

  As the component (d), commercially available products may be used. For example, X-12-981S, X-12-984S, X-12-1154, X-12-1159, KR-513, X-40-1154, X -40-9296, X-41-1805, X-12-972F (both manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.

  (D) A component may be used individually by 1 type and may combine 2 or more types.

  (D) As for content of a component, 1 mass part or more is preferable with respect to 100 mass parts of (a) component, 1-50 mass parts is more preferable, 1-30 mass parts is more preferable, 5-25 mass parts Is particularly preferred.

  The compound containing the structural unit represented by the formula (6) may include a compound in which a ring is formed from the structural unit represented by the formula (6).

  The photosensitive resin composition of the present invention contains a known solvent other than the above components, a coupling agent other than the component (d), a dissolution accelerator, a dissolution inhibitor, a surfactant, a leveling agent, a stabilizer and the like. May be.

Examples of the solvent include organic solvents such as N-methylpyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, propylene glycol monomethyl ether acetate, and ethyl lactate.
A solvent may be used individually by 1 type and may combine 2 or more types.
Although content of a solvent is not specifically limited, Generally, it is 50-1000 mass parts with respect to 100 mass parts of (a) component.

The photosensitive resin composition of the present invention is essentially composed of the components (a) to (d), and optionally a solvent, a coupling agent other than the component (d), a dissolution accelerator, a dissolution inhibitor, a surfactant, It consists of a leveling agent and a stabilizer, and may contain other inevitable impurities as long as the effects of the present invention are not impaired.
In the photosensitive resin composition of the present invention, for example, 80% by mass to 100% by mass, 90% by mass to 100% by mass, 95% by mass to 100% by mass, 98% by mass to 100% by mass, or 100, excluding the solvent. % By mass
(A) to (d) component, or (a) to (d) component, and optionally a coupling agent other than component (d), a dissolution accelerator, a dissolution inhibitor, a surfactant, a leveling agent, and a stabilizer. It may consist of

The cured product of the present invention can be obtained by curing the above-described photosensitive resin composition.
The cured product of the present invention may be used as a pattern cured product or a cured product having no pattern.
As for the film thickness of the hardened | cured material of this invention, 5-20 micrometers is preferable.

  In the method for producing a patterned cured product of the present invention, the above-described photosensitive resin composition is applied on a substrate and dried to form a photosensitive resin film, and the photosensitive resin film is subjected to pattern exposure to form a resin film. A step of developing the resin film after pattern exposure using an alkaline aqueous solution to form a pattern resin film, and a step of heat-treating the pattern resin film to form a pattern cured product.

  A method for producing a cured product having no pattern includes, for example, a step of forming the above-described photosensitive resin film and a step of heat treatment. Furthermore, you may provide the process of exposing.

Examples of the substrate include a glass substrate, a semiconductor substrate such as a Si substrate, a metal oxide insulator substrate such as a TiO ₂ substrate and a SiO ₂ substrate, a silicon nitride substrate, a copper substrate, and a copper alloy substrate.
Although there is no restriction | limiting in particular in the method of application | coating, It can carry out using a spinner etc.

  Drying can be performed using a hot plate, an oven, or the like. The drying temperature is preferably 100 to 150 ° C. The drying time is preferably 30 seconds to 5 minutes. Thereby, the photosensitive resin film can be obtained from the photosensitive resin composition.

  The film thickness of the photosensitive resin film is preferably 5 to 100 μm, more preferably 8 to 50 μm, and still more preferably 10 to 30 μm.

In the pattern exposure, it is preferable to irradiate the photosensitive resin film in a pattern by irradiating actinic rays through a mask.
Examples of the actinic rays to be irradiated include ultraviolet rays such as i rays, visible rays, and radiation, and i rays are preferable. As the exposure apparatus, a parallel exposure machine, a projection exposure machine, a stepper, a scanner exposure machine, or the like can be used.

  When producing a cured product having no pattern, it is preferable to irradiate actinic rays without a mask.

  By developing the resin film after the pattern exposure, a patterned resin film (pattern resin film) can be obtained. Generally, when a positive photosensitive resin composition is used, the exposed portion is removed with a developer.

An aqueous alkali solution can be used as the developer, and examples of the aqueous alkali solution include sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, and the like. Tetramethylammonium hydroxide is preferred.
The concentration of the alkaline aqueous solution is preferably 0.1 to 10% by mass.

The development time is preferably such that the unexposed film thickness after development is 70 to 80% of the film thickness after drying.
Specifically, the developing time varies depending on the component (a) to be used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and further preferably 30 seconds to 4 minutes from the viewpoint of productivity.

  You may add alcohol or surfactant to said developing solution. The addition amount is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the developer.

By heat-treating the pattern resin film, between the two groups selected from one or more acidic functional groups of component (a) and one or more derived substituents thereof, or (a) component and (b) By forming a crosslinked structure between the components and the like, it can be cured to obtain a cured pattern.
Moreover, when (a) component contains a polybenzoxazole precursor, a polybenzoxazole precursor can raise | generate a dehydration ring closure reaction by heat processing, and it can be set as a corresponding polybenzoxazole.

The temperature of the heat treatment is preferably 250 ° C. or less, more preferably 120 to 250 ° C., and further preferably 160 to 230 ° C.
As a result, damage to the substrate and the device can be kept small, the device can be produced with a high yield, and energy saving of the process can be realized.
Moreover, the hardened | cured material which is excellent in adhesiveness with respect to a various board | substrate can be obtained by heat processing at 200 degrees C or less, for example, 175 degreeC.

The heat treatment time is preferably 5 hours or less, more preferably 30 minutes to 3 hours.
Thereby, a crosslinking reaction or a dehydration ring closure reaction can fully advance.

  The atmosphere for the heat treatment may be in the air or in an inert atmosphere such as nitrogen. From the viewpoint of preventing the pattern resin film from being oxidized, a nitrogen atmosphere is preferable.

  Examples of the apparatus used for the heat treatment include a quartz tube furnace, a hot plate, rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace.

The cured product of the present invention can be used as an interlayer insulating film, a cover coat layer, a surface protective film, or the like.
The interlayer insulating film, cover coat layer or surface protective film of the present invention can be used for electronic parts and the like. Thereby, an electronic component with high reliability can be obtained.
The electronic component of the present invention can be used for semiconductor devices and multilayer wiring boards. The semiconductor device and the multilayer wiring board can be used for various electronic devices.
The electronic component of the present invention is not particularly limited except that it has the above-described interlayer insulating film, cover coat layer, or surface protective film, and can have various structures.

1 to 7 are schematic cross-sectional views showing a manufacturing process of a fan-out package having a multilayer wiring structure, which is an embodiment of the electronic component of the present invention. A series of steps from the first step to the seventh step is represented.
FIG. 8 is a schematic cross-sectional view of a fan-out package having a UBM (Under Bump Metal) -free structure, which is an embodiment of the electronic component of the present invention.
The electronic component of the present invention is not limited to the following, and can have various structures.

In these drawings, a semiconductor substrate 1 such as a Si substrate having a circuit element (not shown) is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and the first circuit element is exposed on the first circuit element. A conductor layer 3 is formed.
A film made of polyimide resin or the like is formed thereon as the interlayer insulating film 4 (first step, FIG. 1).

  Next, a photosensitive resin layer 5 such as chlorinated rubber or phenol novolac is formed on the interlayer insulating film 4, and a window 6A is provided by a known method so that a predetermined portion of the interlayer insulating film 4 is exposed. (Second step, FIG. 2).

  The interlayer insulating film 4 exposed in the window 6A portion is selectively etched to form the window 6B. Next, the photosensitive resin layer 5 is removed using an etching solution (third step, FIG. 3).

  Furthermore, the 2nd conductor layer 7 is formed using a well-known method, and the electrical connection with the 1st conductor layer 3 is performed (4th process, FIG. 4). When forming a multilayer wiring structure having three or more layers, the above steps are repeated to form each layer.

  Next, using the above-described photosensitive resin composition, the window 6C is opened by pattern exposure to form the surface protective film 8 (fifth step, FIG. 5). The surface protective film 8 protects the second conductor layer 7 from external stress, α rays, etc., and the obtained semiconductor device is excellent in reliability.

Further, after forming a metal thin film on the surface of the surface protective film 8 by sputtering, a plating resist is formed in accordance with the window 6C using a known method, and the exposed metal thin film portion is plated by UBM (Under). A metal layer 9 called “Bump Metal” is deposited. Then, the plating resist is peeled off, and the metal foil film other than the formation region of the metal layer 9 is removed by etching to form a UBM (sixth step, FIG. 6).
Further, external connection terminals 10 called bumps are formed on the surface of the metal layer 9 (seventh step, FIG. 7). The metal layer 9 is formed for the purpose of relaxing the stress acting on the external connection terminal 10 or for improving the electrical connection reliability.

In FIG. 8, from the viewpoint of reducing the manufacturing cost, in order to omit such a step of forming the metal layer 9 (UBM), the UBM in which the external connection terminal 10 is directly formed after the window 6C is formed in the surface protective film 8 is formed. The free structure is shown.
In the UBM-free structure, it is preferable to form the second conductor layer 7 connected to the external connection terminal 10 thicker than usual in order to suppress an increase in electrical resistance due to the generation of intermetallic compounds.
Furthermore, it is preferable to relieve the stress acting on the external connection terminal 10 with the surface protective film 8. For this reason, it is preferable to form the surface protective film 8 thick in order to cover the thick second conductor layer 7 and increase the stress relaxation ability.

  In the above example, the interlayer insulating film can be formed using the photosensitive resin composition of the present invention.

  Hereinafter, based on an Example and a comparative example, it demonstrates further more concretely about this invention. In addition, this invention is not limited to the following Example.

Synthesis Example 1 (Synthesis of Polymer I)
In a 0.2 liter flask equipped with a stirrer and a thermometer, 60 g of N-methylpyrrolidone was placed, and 13.92 g (38 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added. Added and stirred to dissolve. Subsequently, while maintaining the temperature at 0 to 5 ° C., 7.48 g (28 mmol) of dodecanedioic acid dichloride and 3.56 g (12 mmol) of 4,4′-diphenyl ether dicarboxylic acid dichloride were added dropwise over 10 minutes. The solution was stirred for 60 minutes. The above solution was poured into 3 liters of water, and the precipitate was collected, washed with pure water three times, and then reduced in pressure to obtain polyhydroxyamide (polybenzoxazole precursor) (hereinafter referred to as polymer I and To do).
The weight average molecular weight and dispersion degree of the obtained polymer I were calculated | required on condition of the following by gel permeation chromatograph (GPC) method standard polystyrene conversion. The weight average molecular weight of the polymer I was 33,100, and the degree of dispersion was 2.0.

The measurement conditions of the weight average molecular weight by GPC method are as follows. The measurement was performed using a solution of 1 ml of a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1/1 (volume ratio)] with respect to 0.5 mg of the polymer.
Measuring device: Detector L4000 manufactured by Hitachi, Ltd.
UV pump: L6000 manufactured by Hitachi, Ltd.
C-R4A Chromatopac manufactured by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 × 2
This eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / l), H ₃ PO ₄ (0.06 mol / l)
Flow rate: 1.0 ml / min
Detector: UV270nm

Examples 1-12 and Comparative Examples 1-3
(Preparation of photosensitive resin composition)
Each component was mixed with the component and the compounding quantity shown in Table 1, and the photosensitive resin composition was prepared. The compounding quantity shown in Table 1 is the mass part of each component with respect to 100 mass parts of (a) component.
Each component used in Examples 1 to 12 and Comparative Examples 1 to 3 is as follows. As the component (a), the polymer I obtained in Synthesis Example 1 was used.

(B) Component b-1: Acid-modified alkylated melamine formaldehyde having the following structure (trade name “Cymel 300”, manufactured by Ornex)
b-2: Acid-modified alkylated glycoluril having the following structure (manufactured by Sanwa Chemical Co., Ltd., trade name “MX-270”)

(C) Component c-1: Compound having the following structure

(D) Component Hereinafter, Et is an ethyl group.
The following weight average molecular weights of d-1, d-2, d-4 and d-7 were measured in the same manner as for polymer I. The number average molecular weight of d-3 below was calculated from the structure and the average condensation number.

d-1: X-12-981S (including a structural unit represented by the following formula d-1A and a structural unit represented by the following formula d-1B, the terminal group being represented by a hydroxyl group or the following formula d-1C epoxy equivalent oligomer, relative -Si _{(OEt) 3} is that group: 3, epoxy equivalent: 290 g / mol, viscosity: 1000 mm ² / s, a weight average molecular weight: 870, manufactured by Shin-Etsu Chemical Co., Ltd.)

d-2: X-12-984S (including the structural unit represented by the formula d-1A and the structural unit represented by the formula d-1B, the terminal group is represented by a hydroxyl group or the following formula d-1C epoxy equivalent oligomer, relative -Si _{(OEt) 3} is that group: 3, epoxy equivalent: 270 g / mol, viscosity: 2000 mm ² / s, a weight average molecular weight: 1540, manufactured by Shin-Etsu Chemical Co., Ltd.)

d-3: KR-513 (a mixture of a three-molecule condensate and a four-molecule cyclic condensate of a compound represented by the following d-3A (n1 is 0, 1, 2, or 3), methoxy group: mole of methyl group The ratio is 0.91: 0.09, the alkoxy group amount: 20% by mass, the acrylic equivalent: 210 g / mol, the number average molecular weight: 746.6, manufactured by Shin-Etsu Chemical Co., Ltd.)

d-4: X-12-1154 (an oligomer having a mercapto group and a methoxy group, mercapto equivalent: 240 g / mol, weight average molecular weight: 2510, manufactured by Shin-Etsu Chemical Co., Ltd.)
d-5: X-40-9296 (oligomer having methacryloyl group, methoxy group and methyl group, alkoxy group amount: 22% by mass, methacrylic equivalent: 230 g / mol, viscosity: 20 mm ² / s, manufactured by Shin-Etsu Chemical Co., Ltd. )
d-6: X-41-1805 (an oligomer having a mercapto group, a methoxy group and an ethoxy group, an alkoxy group amount: 50% by mass, a mercapto equivalent: 800 g / mol, a viscosity: 20 mm ² / s, manufactured by Shin-Etsu Chemical Co., Ltd. )
d-7: X-12-972F (an oligomer containing an amino group and an ethoxy group, amino equivalent to -Si (OEt) ₃ : 5, amino equivalent: 600 g / mol, weight average molecular weight: 1650, Shin-Etsu Chemical Co., Ltd. Made)

  The viscosities of d-1, d-2, d-5 and d-6 were measured using an Ubbelohde viscometer.

In the component (d), the group to be contained, the structure of d-1 to d-3, the average condensation number of d-3, the molar ratio of methoxy group: methyl group, the epoxy equivalent to -Si (OEt) _3, and -Si ( The amino equivalent to OEt) ₃ was identified by NMR under the following conditions.

Measuring instrument: AV400M manufactured by Bruker BioSpin
Magnetic field strength: 400MHz
Reference material: Tetramethylsilane (TMS)
Solvent: Dimethyl sulfoxide (DMSO)

  Epoxy equivalent (mass of resin containing 1 equivalent of epoxy group) was determined according to JIS K7236: 2009.

  The acrylic equivalent (mass of resin containing 1 equivalent of acryloyl group) was calculated from (total charged monomer mass (g) + initiator mass (g)) / acrylate amount (mol).

With respect to mercapto equivalent (mass of resin containing 1 equivalent of mercapto group), 0.2 g of sample was precisely weighed, and 20 mL of chloroform was added thereto to prepare a sample solution. Using a starch indicator dissolved in 0.275 g of soluble starch in 30 g of pure water, 20 mL of pure water, 10 mL of isopropyl alcohol, and 1 mL of the starch indicator were added and stirred with a stirrer. An iodine solution (manufactured by Wako Pure Chemical Industries, Ltd., 0.05 mol / L iodine solution, factor: 1.003 (20 ° C.)) was dropped, and the point at which the chloroform layer exhibited a green color was defined as the end point.
From the above measurement, (sample mass (g) × 10000) / (titration amount of iodine solution (ml) × factor of iodine solution) was calculated, and the mercapto equivalent was determined.

  Methacryl equivalent (mass of resin containing 1 equivalent of methacryloyl group) was determined in the same manner as acrylic equivalent.

  The amino equivalent (mass of resin containing 1 equivalent of amino group) was determined by calculating the amine value by neutralization titration.

  The amount of alkoxy groups was measured by NMR under the same conditions as those for measuring the structures of d-1 to d-3.

(Photosensitive characteristic evaluation)
The obtained photosensitive resin composition was spin-coated on a Si substrate, and heated and dried at 110 ° C. for 180 seconds on a hot plate to form a photosensitive resin film having a thickness of 11.0 to 11.5 μm.
The obtained photosensitive resin film was subjected to reduced projection exposure with i-line (365 nm) using an i-line stepper FPA-3000iW (manufactured by Canon Inc.) as a mask. The exposed resin film was developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide. The development time was set to a time during which the film thickness of the unexposed part after development was 70 to 80% of the film thickness after drying.
The resin film after the development was observed by a microscope, the line and space pattern of 3 [mu] m, the case where could be formed at less than 350 mJ / cm ² ○, can not be formed with less than 350 mJ / cm ^2, it can be formed at 350 mJ / cm ² or more The case was marked with x.

(Manufacture of cured product)
The above-mentioned photosensitive resin composition was spin-coated on a Si substrate, and heated and dried at 110 ° C. for 180 seconds on a hot plate to form a photosensitive resin film having a size of 15.0 to 16.0 μm.
The obtained photosensitive resin film was subjected to broadband (BB) exposure using a mask aligner MA-8 (manufactured by SUSS Microtec), and the exposed resin film was 2.38 mass of tetramethylammonium hydroxide. A 10% width strip-shaped pattern resin film was obtained by developing with a% aqueous solution.
The obtained pattern resin film was cured at 200 ° C. for 1 hour to obtain a pattern cured product having a thickness of 10 μm.

(Mechanical property evaluation)
The obtained pattern cured product was immersed in a 4.9% by mass hydrofluoric acid aqueous solution, and the 10 mm width cured product was peeled from the wafer.
About the peeled 10 mm width hardened | cured material, the tension test was done using Autograph AGS-X100N (made by Shimadzu Corporation). The distance between chucks was 20 mm, the tensile speed was 5 mm / min, the measurement temperature was 18 to 25 ° C., and each cured product of each Example and Comparative Example was measured three times to obtain an average value of 1.
Moreover, the above-mentioned pattern cured product is used as a PCT test apparatus HAS.
Using TEST (Hirayama Seisakusho Co., Ltd., PC-R8D), it was treated at 121 ° C., 100 RH (Relativistic Humidity)%, 2 atm for 100 hours.
The pattern cured product was taken out from the PCT test apparatus, the pattern cured product was peeled off in the same manner as described above, and a tensile test was performed to obtain an average value of 2.
The average value 2 was subtracted from the average value 1 and divided by the average value 1, and the percentage value was less than 30%, and the case where it was 30% or more was marked as x. The results are shown in Table 1.

  The photosensitive resin composition of the present invention can be used for electronic parts and the like.

DESCRIPTION OF SYMBOLS 1 Semiconductor substrate 2 Protective film 3 1st conductor layer 4 Interlayer insulating film 5 Photosensitive resin layer 6A, 6B, 6C Window 7 2nd conductor layer 8 Surface protective film 9 Metal layer 10 External connection terminal

Claims (9)

(A) a polymer having an acidic functional group or a derivative substituent thereof;
(B) a crosslinking agent;
(C) a photosensitizer;
(D) having one or more functional groups, wherein the functional group is composed of a methyl group, a phenyl group, an epoxy group, a mercapto group, an amino group, an isocyanate group, a vinyl group, an acryloyl group, a methacryloyl group, and an allyl group. The photosensitive resin composition containing the silane coupling agent which is 1 or more selected.   The photosensitive resin composition according to claim 1, wherein the component (a) is one or more selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a copolymer thereof. The photosensitive resin composition of Claim 1 or 2 in which the said (a) component has a structural unit represented by following formula (1).
(In Formula (1), U is a divalent organic group, a single bond, —O— or —SO ₂ —, and V is a divalent organic group.)   The photosensitive resin composition according to claim 1, wherein the component (d) has a weight average molecular weight of 150 or more.   Content of the said (d) component is 1 mass part or more with respect to 100 mass parts of said (a) component, The photosensitive resin composition in any one of Claims 1-4. Applying the photosensitive resin composition according to any one of claims 1 to 5 on a substrate and drying to form a photosensitive resin film;
Forming a resin film by pattern exposure of the photosensitive resin film;
Developing the resin film after the pattern exposure using an alkaline aqueous solution, and forming a pattern resin film;
And a step of heat-treating the pattern resin film to form a pattern cured product.   Hardened | cured material which hardened the photosensitive resin composition in any one of Claims 1-5.   An interlayer insulating film, a cover coat layer or a surface protective film produced using the cured product according to claim 7.   An electronic component comprising the interlayer insulating film, cover coat layer or surface protective film according to claim 8.