JP2011123219A - Photosensitive polyamide resin composition, method for forming cured relief pattern and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive polyamide resin composition having excellent resist stripping liquid resistance, excellent reflow resistance and good adhesion to an underfill layer and a silicon substrate. <P>SOLUTION: The photosensitive polyamide resin composition includes 100 pts.mass of (A) a polyamide resin including a repeating unit represented by formula (1), 0.5-20 pts.mass of (B) a photoinitiator, and 0.1-25 pts.mass of (C) an organosilicon compound having a group capable of reacting with an epoxy resin under heat; wherein X<SP>1</SP>is a 6-15C trivalent organic group; k is 0 or 2; Y is a 6-35C divalent organic group in the case of k=0 and a 6-35C tetravalent organic group in the case of k=2; X<SP>2</SP>is a 6-35C tetravalent organic group ; X<SP>3</SP>is a 6-15C divalent organic group and may be the same or different; l, m and n are an integer and have the relationship of 0.05≤1/(l+m+n)≤1, provided that (l+m+n) equals an integer of 2-150; R<SP>1</SP>and R<SP>2</SP>are an aliphatic group having at least one 5-20C radical polymerizable unsaturated bond group which may contain an atom other than carbon, and R<SP>1</SP>and R<SP>2</SP>may be the same or different. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photosensitive polyamide resin composition that is a precursor of a heat-resistant resin used as a surface protective film or an interlayer insulating film of a semiconductor device. Specifically, even when the curing temperature is low, the photosensitive polyamide resin has a high heat resistance and chemical resistance and can provide a cured relief pattern having good adhesion to a thermosetting resin such as an underfill layer. It is a composition. In addition, the present invention relates to a method for forming a heat-resistant cured relief pattern using the photosensitive polyamide resin composition, and a semiconductor device having the cured relief pattern.

Polyimide resins having excellent heat resistance, electrical properties, and mechanical properties are widely used for insulating materials for electronic parts and surface protection films, interlayer insulation films, and α-ray shielding films for semiconductor devices. . (For example, see Patent Document 1 below.)
By the way, a semiconductor device (hereinafter, also referred to as “element”) is mounted on a printed circuit board by various methods according to the purpose. However, along with recent high integration of semiconductor elements and miniaturization of element package shapes, Area array type mounting methods such as a flip chip method that conducts by reflow connection via a bump electrode formed on the surface of the element via a redistribution layer from a wire bonding method that connects the lead frame and the element with a thin wire Is becoming mainstream.

  In such a mounting method using bump electrodes, a chip, a rewiring layer, a heat-resistant polyimide resin film, an adhesive, a substrate, and the like are laminated. In particular, the heat-resistant polyimide resin film and bumps between each layer are protected. The importance of adhesion to an underfill layer is increasing. Specifically, if the adhesion between these layers is poor, peeling occurs at the interface due to the difference in residual stress between different materials, and damage to the bump electrode and rewiring layer may cause malfunction due to poor conduction or short circuit. Cause. For example, there are the following prior art documents relating to this problem (Patent Documents 2 and 3).

  On the other hand, photosensitive polyimide resin for materials of surface-mount type semiconductor elements needs excellent chemical resistance in each process of forming bump electrode structure in addition to excellent pattern formability and heat resistance. Is done. Specifically, a stripping solution for stripping a resist used for forming a rewiring layer, an etching solution used for forming a metal wiring layer such as Al, Ti, and Cu, a flux used in a solder electrode formation (reflow) process, and a cleaning solution therefor Must have good resistance to This is because the pattern shape does not change in such a process, and if a deteriorated layer is formed on the film surface, the adhesiveness with the underfill layer is lowered, which causes peeling. Although efforts have been made to improve mechanical properties, heat resistance, and chemical resistance by devising the polymer skeleton structure and composition additives, as far as the present inventors know, adhesion to the underfill layer has not been studied at all. . That is, the present situation is that the material design that can answer the resist stripping solution resistance, the reflow resistance, and the adhesion with the underfill layer required for the recent semiconductor element package as described above has not been made.

Japanese Patent Laid-Open No. 6-342211 JP 2004-331908 A JP 2004-59440 A

  That is, the problem to be solved by the present invention is to provide a photosensitive resin composition which is excellent in resist stripping solution resistance and reflow resistance and has good adhesion to an underfill layer and a silicon substrate. Furthermore, it is a problem to be solved by the present invention to provide a method for forming a cured relief pattern using the photosensitive resin composition and a semiconductor device having a cured relief pattern formed by the method.

  As a result of intensive investigations to solve the above problems, the present inventors have determined that a photosensitive resin composition containing a specific organosilicon compound based on a polyamide produced by containing a specific raw material by copolymerization. As a result, it was discovered that the above problems could be solved, and the present invention was completed. Specifically, the present invention is as the following [1] to [7].

[1] (A) The following general formula (1):

{In the formula, X ¹ is a trivalent organic group having 6 to 15 carbon atoms, k is 0 or 2, and Y is a divalent organic group having 6 to 35 carbon atoms when k = 0. Yes, when k = 2, it is a tetravalent organic group having 6 to 35 carbon atoms, X ² is a tetravalent organic group having 6 to 35 carbon atoms, and X ³ is a carbon number having 6 to 15 carbon atoms. It is a divalent organic group, which may be the same or different, l, m and n are integers, have a relationship of 0.05 ≦ l / (l + m + n) ≦ 1, and (l + m + n) is R is an integer of ^{2 to} 150, and R ¹ and R ² are aliphatic groups having at least one radical-polymerizable unsaturated bond group having 5 to 20 carbon atoms, which may contain atoms other than carbon. , May be the same or different. } 100 parts by mass of a polyamide resin including a repeating unit represented by: (B) 0.5 to 20 parts by mass of a photoinitiator, and (C) an organosilicon having at least one group capable of reacting with an epoxy resin by heat A photosensitive polyamide resin composition comprising 0.1 to 25 parts by mass of a compound.

[2] The organic groups X ¹ , X ² , X ³ , and Y in the formula (1) are each independently an aromatic group, an alicyclic group, an aliphatic group, a siloxane group, or a group having a composite structure thereof. The photosensitive polyamide resin composition according to [1], which is a group selected from any one of the above.

  [3] A group selected from the group consisting of a carboxyl group, a carboxylic acid anhydride group, a sulfonyl group, an oxirane group and an amino group, wherein the organosilicon compound having at least one group capable of reacting with an epoxy resin by heat (C) Or a photosensitive polyamide resin composition according to [1] or [2], which is an organosilicon compound having at least one group protecting it.

｛式中、ｇは１または２の整数であり、Ｚは、ｇが１のとき２価の芳香族基、脂環式基、脂肪族基のいずれかより選択される基であり、ｇが２のとき４価の芳香族基である。Ｇはケイ素原子に直接結合する炭素原子を含む２価の有機基であり、ｄは０または１の整数である。Ｒ^４及びＲ^５は同一でも異なっていてもよい、炭素数１〜４のアルキル基であり、ｅは０または１の整数である。Ｒ^３は水素原子または１価の炭化水素基である。｝で表されることを特徴とする、［１］又は［２］に記載の感光性ポリアミド樹脂組成物。 [4] (C) An organosilicon compound having at least one group capable of reacting with an epoxy resin by heat is represented by the following general formula (2):

{In the formula, g is an integer of 1 or 2, Z is a group selected from a divalent aromatic group, an alicyclic group, and an aliphatic group when g is 1, and g is When it is 2, it is a tetravalent aromatic group. G is a divalent organic group containing a carbon atom directly bonded to a silicon atom, and d is an integer of 0 or 1. R ⁴ and R ⁵ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and e is an integer of 0 or 1. R ³ is a hydrogen atom or a monovalent hydrocarbon group. } The photosensitive polyamide resin composition as described in [1] or [2] characterized by the above-mentioned.

  [5] A photosensitive polyamide resin composition solution obtained by dissolving the photosensitive polyamide resin composition according to any one of [1] to [4] above in a solvent.

  [6] The photosensitive polyamide resin composition according to any one of [1] to [4] above or the photosensitive polyamide resin composition solution according to [5] is applied onto a substrate to form a coating film. A method of forming a cured relief pattern by forming and exposing the coating film directly or through a patterning mask, developing the coating film using a developer, and then heat-curing.

  [7] A semiconductor device having a cured relief pattern obtained by the method according to [6] above.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which is excellent in resist stripping liquid tolerance and reflow tolerance, and has favorable adhesiveness to an underfill layer and a silicon base material is provided. Furthermore, a method for forming a cured relief pattern using the photosensitive resin composition and a semiconductor device having a cured relief pattern formed by the method are also provided.

  Specifically, the photosensitive resin composition provided by the present invention is based on polyamide manufactured by copolymerizing a specific raw material with a polyimide precursor, and contains a specific organosilicon compound. Excellent resistance to resist stripping solution and good adhesion to underfill layer and element chip. When the photosensitive resin composition is prepared using an area array type semiconductor device such as a flip chip system, an effect that high operational reliability can be obtained over a long period of time is obtained.

  Hereinafter, embodiments of the present invention will be described in detail. In each of the formulas described in this specification, the structures represented by the same reference numerals when there are a plurality of them in the molecule may be one type or a combination of two or more types.

<(A) Polyamide resin>
The polyamide resin that is a component of the photosensitive polyamide resin composition of the present invention has the following general formula (1):

{In the formula, X ¹ is a trivalent organic group having 6 to 15 carbon atoms, k is 0 or 2, and Y is a divalent organic group having 6 to 35 carbon atoms when k = 0. Yes, when k = 2, it is a tetravalent organic group having 6 to 35 carbon atoms, X ² is a tetravalent organic group having 6 to 35 carbon atoms, and X ³ is a carbon number having 6 to 15 carbon atoms. Divalent organic group, which may be the same or different, 0.05 ≦ l / (l + m + n) ≦ 1, (l + m + n) is an integer of ^{2 to} 150, and R ¹ and R ² Is an aliphatic group which may contain atoms other than carbon and has at least one radical-polymerizable unsaturated bond group having 5 to 20 carbon atoms, and may be the same or different. } Is a polyamide resin including a repeating unit represented by:

  When the repeating number 1 in the formula (1) includes 5% or more of the total number of all structural units constituting the polyamide resin, an effect of copolymerizing various structures represented by the repeating number 1 can be obtained. In the above formula (1), the arrangement of the structures having the repeating numbers 1 and m and n may be random copolymerization or block copolymerization.

  In the formula (1), l is an integer of 1 or more, and (l + m + n) is an integer of 2 to 150 at the same time. When (l + m + n) is 2 or more, the requirements as a polymer expected by the present invention are satisfied, and when it is 150 or less, when a photosensitive resin composition is used, the solubility when diluted in a solvent, Excellent in terms of speed. (L + m + n) is preferably 4 to 150, and more preferably 4 to 100.

  In the photosensitive polyamide resin composition of the present invention, 0.05 ≦ l / (l + m + n) ≦ 1. If this value is 0.05 or more, the present invention is expected not only to have excellent reflow resistance and resist stripping solution resistance of the coating film made of the photosensitive resin composition of the present invention, but also to adhere to the underfill layer. Can be improved to the extent of The ratio is preferably 0.05 or more, and more preferably 0.1 or more.

  In the photosensitive polyamide resin composition of the present invention, the ratio of m / (l + m + n) out of the total number of all structural units constituting the polyamide resin is 0.95 or less when 0.05 ≦ l / (l + m + n). If it is 1 / (l + m + n) ≦ 0.30 from the viewpoint of sensitivity, it is 0.10 or more, more preferably 0.20 or more, from the viewpoint of sensitivity, the photosensitive resin composition of the present invention. It is excellent in the photosensitive property of the coating film.

In the above formula (1), R ¹ and R ² are aliphatic groups having 5 to 20 carbon atoms which may contain atoms other than carbon and have at least one radical polymerizable unsaturated bond group. . R ¹ is represented by the following formula (3) from the viewpoint of photosensitive characteristics and chemical resistance:

{In the formula, R ⁶ is a C 4-19 aliphatic group having at least one radical-polymerizable unsaturated bond group. } Is preferable.

From the viewpoint of further improving the photosensitive properties, R ¹ and R ² are preferably groups having at least one (meth) acryloyloxymethyl group.

In the above formula (1), the trivalent organic group represented by X ¹ is a trivalent organic group having 6 to 15 carbon atoms from the viewpoint of photosensitive properties, mechanical properties, heat resistance, chemical resistance, and the like. . In formula (1), the divalent or tetravalent organic group represented by Y is an organic group having 6 to 35 carbon atoms from the viewpoints of photosensitive characteristics, mechanical properties, heat resistance, chemical resistance, and the like. In addition, in formula (1), the tetravalent organic group represented by X ² is a tetravalent organic group having 6 to 35 carbon atoms from the viewpoint of photosensitive properties, mechanical properties, heat resistance, chemical resistance, and the like. is there. X ² is a structure obtained by removing two esterified carboxyl group-derived moieties and two carboxyl group-derived moieties from the structure of tetracarboxylic acid or a derivative thereof. In formula (1), the divalent organic group represented by X ³ is a divalent organic group having 6 to 15 carbon atoms from the viewpoint of photosensitive properties, heat resistance, chemical resistance, and the like. X ³ does not contain a —NH—R ¹ group and has a structure obtained by removing two carboxyl group-derived moieties from the structure of dicarboxylic acid or a derivative thereof.

In the present invention, X ¹ , X ² , X ³ and Y are each independently an aromatic group, an alicyclic group, an aliphatic group, from the viewpoint of photosensitive properties, mechanical properties, heat resistance, chemical resistance, and the like. It is preferably a group selected from the group consisting of group groups, siloxane groups and groups of their composite structure.

In the above formula (1), X ¹ has the following structure:

  The aromatic group is more preferably an aromatic group selected from the group consisting of groups represented by the formula (1), and more preferably an aromatic group obtained by removing a carboxyl group and an amino group from an amino group-substituted isophthalic acid structure.

  In formula (1), Y is more preferably a cyclic organic group having 1 to 4 aromatic or aliphatic rings which may be substituted, an aliphatic group or a siloxane group. Specifically, preferred examples of the cyclic organic group include the following aromatic groups or alicyclic groups:

  (In the formula, each A is independently a group selected from the group consisting of a hydroxyl group, a methyl group, an ethyl group, a propyl group, and a butyl group. In the propyl group and butyl group, various isomers are also represented. Including)

  {Wherein, p and q are each independently an integer of 0 to 3, r is an integer of 0 to 8, s and t are each independently an integer of 0 to 10, and B is a methyl group, ethyl Group, propyl group, butyl group or isomers thereof. }. In the above substituent group, p and q each represent the number of repeating methylene chains, r, s and t each represent the number of substituents on the ring of substituent B, and B represents the substituent on the ring, particularly the number of carbon atoms. 1 to 4 hydrocarbon groups are represented.

  Moreover, as a preferable example of an aliphatic group or a siloxane group, the following:

{Wherein, a is an integer of 2 to 12, b is an integer of 1 to 3, c is an integer of 1 to 20, and R ³ and R ⁴ each independently represent 1 to 3 carbon atoms. Or an optionally substituted phenyl group. } Group.

X ² in formula (1) is preferably an aromatic group, an aliphatic group or an alicyclic group, respectively. Preferred aromatic groups are the following groups:

  Is mentioned.

X ³ in formula (1) is preferably an aromatic group, an aliphatic group or an alicyclic group, respectively. Preferred aromatic groups are the following groups:

  Is mentioned.

  The polyamide resin of the present invention can be synthesized, for example, as follows.

<Synthesis of sealed phthalic acid compound>
First, a compound having a trivalent aromatic group X ¹ (a group corresponding to X ¹ in the above formulas), for example, phthalic acid substituted with an amino group, isophthalic acid substituted with an amino group, and 1 mol or more of a compound selected from the group consisting of terephthalic acid substituted with an amino group (hereinafter referred to as “phthalic acid compound”) and 1 mol of one or more compounds that react with an amino group Then, a compound in which the amino group of the phthalic acid compound is modified and sealed with one or more groups containing a radical polymerizable unsaturated bond described below (hereinafter referred to as “phthalic acid compound sealing body”) is synthesized. To do.

  A structure in which a phthalic acid compound is sealed with a group containing the above-mentioned radical polymerizable unsaturated bond can impart negative photosensitivity (that is, photocuring property) to the polyamide resin. The group containing a radically polymerizable unsaturated bond is preferably an aliphatic group having 5 to 20 carbon atoms having a radically polymerizable unsaturated bond group from the viewpoint of photosensitive properties and chemical resistance, and methacryloyloxymethyl. Particularly preferred are aliphatic groups containing groups and / or acryloyloxymethyl groups.

  The above-mentioned sealed phthalic acid compound is an aliphatic acid chloride, aliphatic isocyanate or aliphatic epoxy compound having 5 to 20 carbon atoms having at least one amino group of the phthalic acid compound and a radical polymerizable unsaturated bond group. It can obtain by making it react with. Suitable aliphatic acid chlorides include 2-[(meth) acryloyloxy] acetyl chloride, 3-[(meth) acryloyloxy] propionyl chloride, 2-[(meth) acryloyloxy] ethyl chloroformate, 3- [ (Meth) acryloyloxypropyl] chloroformate and the like. Suitable aliphatic isocyanates include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxymethyl] ethyl isocyanate, 2- [2- (meth) acryloyloxyethoxy] ethyl isocyanate] and the like Is mentioned. Suitable aliphatic epoxy compounds include glycidyl (meth) acrylate and the like. These may be used alone or in combination of two or more. It is particularly preferred to use 2-methacryloyloxyethyl isocyanate.

  Furthermore, as the phthalic acid compound encapsulant, one in which the phthalic acid compound is 5-aminoisophthalic acid is preferable because a polyamide resin having excellent photosensitivity and excellent film characteristics after heat curing can be obtained. .

  The sealing reaction proceeds by stirring and dissolving and mixing the phthalic acid compound and the sealing agent in a reaction solvent in the presence of a basic catalyst such as pyridine or a tin-based catalyst such as di-n-butyltin dilaurate. be able to.

  As the reaction solvent, those that completely dissolve the product phthalic acid compound encapsulated body are preferable. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide , Tetramethylurea, gamma butyrolactone and the like.

  Other reaction solvents include ketones, esters, lactones, ethers, halogenated hydrocarbons and hydrocarbons, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate. , Butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene, etc. Is mentioned. These solvents may be used alone or in admixture of two or more as required.

  Depending on the type of sealing agent, such as acid chloride, hydrogen chloride may be produced as a by-product during the sealing reaction. In this case, from the viewpoint of preventing contamination in subsequent processes, the product is once again re-precipitated in water, washed with water and dried, or passed through a column filled with an ion exchange resin to reduce or reduce ionic components. It is preferable to carry out.

<Synthesis of polyamide resin>
Second, the phthalic acid compound encapsulated body and a diamine compound having a divalent or tetravalent organic group Y (a group corresponding to Y in each of the above-mentioned formulas) are converted into a basic catalyst such as pyridine or triethylamine. The polyamide resin of the present invention can be obtained by mixing in an appropriate solvent in the presence and amide polycondensation.

If desired, a part of the encapsulated phthalic acid compound may be a tetracarboxylic acid having a tetravalent organic group X ² (a group corresponding to X ² in the above formula (1)) or an anhydride thereof, and a divalent A dicarboxylic acid having an organic group X ³ (a group corresponding to X ³ in the above formula (1)) may be used in combination.

A compound having a tetravalent organic group X ² (a group corresponding to X ² in each of the above formulas) reacts a tetracarboxylic dianhydride containing a tetravalent organic group X ² with an alcohol. And can be obtained by adjusting as a half acid / half ester body. Examples of the method of reacting tetracarboxylic dianhydride and alcohol include a method in which the esterification reaction proceeds by stirring and dissolving in an appropriate solvent and mixing in the presence of a basic catalyst such as pyridine. Any means can be used. Suitable reaction solvents are preferably those in which the half acid / half ester is completely dissolved, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethyl Examples include urea and gamma butyrolactone.

Examples of the tetracarboxylic acid having tetravalent organic group X ² or a compound suitably used as an anhydride thereof include pyromellitic anhydride, diphenyl ether-3,3′-4, 4′-tetracarboxylic anhydride, Benzophenone-3,3′-4,4′-tetracarboxylic anhydride, biphenyl-3,3′-4,4′-tetracarboxylic anhydride, diphenylsulfone-3,3′-4,4′-tetra Carboxylic anhydride, diphenylmethane-3,3′-4,4′-tetracarboxylic anhydride, 2,2-bis (3,4-phthalic anhydride) propane, 2,2-bis (3,4-anhydride) Phthalic acid) 1,1,1,3,3,3, hexafluoropropane and the like. Of course, these can be used alone or in combination of two or more.

Alcohols used in the esterification reaction of tetracarboxylic dianhydride as a raw material for the tetravalent organic group X ² are alcohols having an olefinic double bond. Specifically, 2-methacryloyloxyethyl alcohol, 2-acryloyloxyethyl alcohol, 1-acryloyloxy-2-propyl alcohol, 2-methacrylamide ethyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl Vinyl ketone, 2-hydroxyethyl methacrylate, 2-hydroxypropyl-acrylate, 2-hydroxypropyl-methacrylate, 2-hydroxybutyl-acrylate, 2-hydroxybutyl-methacrylate, 2-hydroxy-3-methoxypropyl-acrylate, 2- Hydroxy-3-methoxypropyl-methacrylate, 2-hydroxy-3-butoxypropyl-acrylate, 2-hydroxy-3-butoxypropyl-methacrylate 2-hydroxy-3-phenoxypropyl-acrylate, 2-hydroxy-3-phenoxypropyl-methacrylate, 2-hydroxy-3-t-butoxypropyl-acrylate, 2-hydroxy-3-t-butoxypropyl-methacrylate, 2 -Hydroxy-3-cyclohexylalkoxypropyl-acrylate, 2-hydroxy-3-cyclohexyloxypropyl-methacrylate, 2-hydroxy-3-cyclohexyloxypropyl-acrylate, 2-methacryloxyethyl-2-hydroxypropyl phthalate, 2-acrylic Examples include loxyethyl-2-hydroxypropyl phthalate, glycerin diacrylate, and glycerin dimethacrylate. These alcohols can be used alone or in admixture of two or more.

  In addition, as described in JP-A-6-807776, a part of methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, allyl alcohol and the like are mixed with the alcohol having the olefinic double bond. It can also be used.

  Theoretically, the amount of alcohols used for esterification of tetracarboxylic dianhydride is 1.0 equivalent with respect to 1.0 equivalent of tetracarboxylic dianhydride. Storage stability of the photosensitive polyamic acid ester composition finally obtained by synthesizing tetracarboxylic acid diester with alcohol to 1.01 to 1.10 equivalent to 1.0 equivalent of dianhydride This is preferable because of improved properties.

Examples of the dicarboxylic acid having the divalent organic group X ³ include phthalic acid, isophthalic acid, terephthalic acid, 4,4′-diphenyl ether dicarboxylic acid, 3,4′-diphenyl ether dicarboxylic acid, and 3,3′-diphenyl ether dicarboxylic acid. 4,4'-biphenyldicarboxylic acid, 3,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-benzophenone dicarboxylic acid, 3,4'-benzophenone dicarboxylic acid, 3,3 ' -Benzophenone dicarboxylic acid, 4,4'-hexafluoroisopropylidene dibenzoic acid, 4,4'-dicarboxydiphenylamide, 1,4-phenylenediethanic acid, 1,1-bis (4-carboxyphenyl) -1 -Phenyl-2,2,2-trifluoroethane, bis (4-carboxyphenyl) sulfide, (4-carboxyphenyl) tetraphenyldisiloxane, bis (4-carboxyphenyl) tetramethyldisiloxane, bis (4-carboxyphenyl) sulfone, bis (4-carboxyphenyl) methane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, N- (3,5-di Carboxyphenyl) -N′-ethoxycarbonylurea, N- (3,5-dicarboxyphenyl) norborneneimide, 2,2-bis- (p-carboxyphenyl) propane, 4,4 ′-(p-phenylenedioxy ) Aromatic dica such as dibenzoic acid and 2,6-naphthalenedicarboxylic acid In addition to rubonic acid, succinic acid, adipic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, malic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 5-norbornene-2,3- Aliphatic dicarboxylic acids such as dicarboxylic acids and alicyclic dicarboxylic acids.

  The diamine compound having the organic group Y is at least one selected from the group consisting of aromatic diamine compounds, aromatic bisaminophenol compounds, alicyclic diamine compounds, linear aliphatic diamine compounds, and siloxane diamine compounds. Diamine compounds are preferred, and multiple types can be used in combination as desired.

  Examples of the aromatic diamine compound include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, 3,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'- Diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane , 3,4'-di Minodiphenylmethane, 3,3′-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, Bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3 -Aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenyl) benzene, 1,3 -Bis (4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) anthracene, 2,2-bis ( -Aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4- Aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, ortho-tolidine sulfone, 9,9-bis (4-aminophenyl) fluorene, and hydrogen on these benzene rings Examples thereof include diamine compounds in which some of the atoms are substituted with one or more groups selected from the group consisting of a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, and a halogen atom.

  Examples of diamine compounds in which hydrogen atoms on the benzene ring are substituted include 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3, 3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro- 4,4′-diaminobiphenyl and the like can be mentioned.

  Aromatic bisaminophenol compounds include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-dihydroxy-4,4′-diaminodiphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (3-hydroxy-4-aminophenyl) hexafluoropropane, bis- (3-hydroxy-4-aminophenyl) methane, 2,2-bis- (3-hydroxy-4-aminophenyl) Propane, 3,3′-dihydroxy-4,4′-diaminobenzophenone, 3,3′-dihydroxy-4,4′-di Minodiphenyl ether, 4,4′-dihydroxy-3,3′-diaminodiphenyl ether, 2,5-dihydroxy-1,4-diaminobenzene, 4,6-diaminoresorcinol, 1,1-bis (3-amino- 4-hydroxyphenyl) cyclohexane, 4,4- (α-methylbenzylidene) -bis (2-aminophenol) and the like.

  Examples of the alicyclic diamine compound include 1,3-diaminocyclopentane, 1,3-diaminocyclohexane, 1,3-diamino-1-methylcyclohexane, 3,5-diamino-1,1-dimethylcyclohexane, 1,5 -Diamino-1,3-dimethylcyclohexane, 1,3-diamino-1-methyl-4-isopropylcyclohexane, 1,2-diamino-4-methylcyclohexane, 1,4-diaminocyclohexane, 1,4-diamino-2 , 5-diethylcyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 2- (3-aminocyclopentyl) -2-propylamine, mensendiamine, isophoronediamine, norbornane Diamine, 1-cycloheptene-3,7-diamine, , 4′-methylenebis (cyclohexylamine), 4,4′-methylenebis (2-methylcyclohexylamine), 1,4-bis (3-aminopropyl) piperazine, 3,9-bis (3-aminopropyl) -2 4,8,10-tetraoxaspiro- [5,5] -undecane and the like.

  Examples of linear aliphatic diamine compounds include 1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, and 1,12-diaminododecane. And hydrocarbon type diamines such as 2- (2-aminoethoxy) ethylamine, 2,2 ′-(ethylenedioxy) diethylamine, and bis [2- (2-aminoethoxy) ethyl] ether. Can be mentioned.

  Examples of the siloxane diamine compound include dimethyl (poly) siloxane diamine, for example, trade names PAM-E, KF-8010, and X-22-161A manufactured by Shin-Etsu Chemical Co., Ltd.

Examples of the amide polycondensation method include dicarboxylic acid components (phthalic acid compound encapsulated bodies, tetracarboxylic acid half-acid / half-ester bodies having a tetravalent organic group X ² , and divalent organic groups X ^3. A dicarboxylic acid having a carboxylic acid; the same applies hereinafter) to a symmetric polyanhydride using a dehydrating condensing agent, and then mixed with a diamine compound. The dicarboxylic acid component is acid chlorided by a known method and then mixed with the diamine compound. Examples thereof include a method of reacting a dicarboxylic acid component and an active esterifying agent in the presence of a dehydrating condensing agent to form an active ester, and then mixing the product with a diamine compound.

  Preferred dehydrating condensation agents include, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1′-carbonyldioxy-di-1,2,3-benzotriazole, N, N'-disuccinimidyl carbonate etc. are mentioned.

  Examples of the chlorinating agent include thionyl chloride.

  Examples of active esterifying agents include N-hydroxysuccinimide, 1-hydroxybenzotriazole, N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide, 2-hydroxyimino-2-cyanoacetic acid ethyl, 2-hydroxyimino- Examples include 2-cyanoacetamide.

  As the reaction solvent, a solvent that completely dissolves the polymer to be produced is preferable. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma butyrolactone Etc.

  In addition, ketones, esters, lactones, ethers, hydrocarbons, halogenated hydrocarbons and the like may be used as a reaction solvent depending on circumstances. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichloro Examples include butane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene and the like.

  After completion of the amide polycondensation reaction, the precipitate derived from the dehydration condensing agent that has precipitated in the reaction solution is filtered off as necessary. Next, a poor polyamide solvent such as water, an aliphatic lower alcohol or a mixture thereof is added to the reaction solution to precipitate the polyamide. Further, the precipitated polyamide is redissolved in a solvent and purified by repeating the reprecipitation precipitation, followed by vacuum drying to isolate the target polyamide. In order to further improve the degree of purification, this polyamide solution may be passed through a column packed with an ion exchange resin to remove ionic impurities.

  The weight average molecular weight in terms of polystyrene by gel permeation chromatography (hereinafter referred to as “GPC”) of the polyamide resin of the present invention is preferably from 7,000 to 70,000, and from 10,000 to 50,000. Is more preferable. When the weight average molecular weight in terms of polystyrene is 7,000 or more, the basic physical properties of the cured relief pattern are good. Moreover, if the polystyrene conversion weight average molecular weight is 70,000 or less, the development solubility at the time of forming a relief pattern is good.

  Tetrahydrofuran and N-methyl-2-pyrrolidone are recommended as eluents for GPC. Moreover, a weight average molecular weight value is calculated | required from the calibration curve created using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.

<(B) Photoinitiator>
Examples of the photoinitiator that is a component of the photosensitive polyamide resin composition of the present invention include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenylketone, dibenzylketone, and fluorenone. Acetophenone derivatives such as 2,2′-diethoxyacetophenone and 2-hydroxy-2-methylpropiophenone, thioxanthone derivatives such as 1-hydroxycyclohexyl phenyl ketone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and diethylthioxanthone, Benzyl derivatives such as benzyl, benzyldimethyl ketal and benzyl-β-methoxyethyl acetal, benzoin derivatives such as benzoin methyl ether, 2,6-di (4′-diazidobenzal) -4- Azides such as tilcyclohexanone, 2,6′-di (4′-diazidobenzal) cyclohexanone, 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenylpropanedione-2- ( O-methoxycarbonyl) oxime, 1-phenylpropanedione-2- (O-ethoxycarbonyl) oxime, 1-phenylpropanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanetrione-2- (O -Ethoxycarbonyl) oxime, oximes such as 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime, N-arylglycines such as N-phenylglycine, peroxides such as benzoyl peroxide , Aromatic biimidazoles, titanocenes, etc. are used The oximes are preferred in view of curability and photosensitivity of a thick film.

  As for the addition amount of these photoinitiators, 0.5-20 mass parts is preferable with respect to 100 mass parts of (A) polyamide resin. Addition of 0.5 parts by mass or more of the photoinitiator to 100 parts by mass of the polyamide resin provides excellent photosensitivity, and addition of 20 parts by mass or less provides excellent thick film curability.

<(C) Organosilicon compound having at least one group capable of reacting with epoxy resin by heat>
Preferable examples of the organosilicon compound having at least one group capable of reacting with an epoxy resin by heat, which is a component of the photosensitive polyamide resin composition of the present invention, include an amino group, an oxirane group, a carboxyl group, and a carboxyl group. An organosilicon compound having at least one group selected from the group consisting of an acid anhydride group and a sulfonyl group, or a group protecting the group is particularly preferred. Since the base material of the underfill is an epoxy resin, it is preferable to have a group that can react with the epoxy resin by heat from the viewpoint of adhesion to the underfill.

  Examples of the (dialkoxy) monoalkylsilyl compound and (trialkoxy) silyl compound having an amino group (hereinafter, the notation of alkoxy indicates a methoxy group or an ethoxy group): 2-aminoethyltrialkoxysilane, 3 -Aminopropyltrialkoxysilane, 3-aminopropyl dialkoxymethylsilane, 2-aminoethylaminomethyltrialkoxysilane, 2-aminoethylaminomethyl dialkoxymethylsilane, 3- (2-aminoethylaminopropyl) trialkoxysilane 3- (2-aminoethylaminopropyl) dialkoxymethylsilane, 3-allylaminopropyltrialkoxysilane, 2- (2-aminoethylthioethyl) trialkoxysilane, 2- (2-aminoethylthioethyl) dialkoxy Methylsilane, 3-piperazino-propyl tri alkoxysilanes, 3-piperazino-propyl di alkoxide methyl silane, cyclohexyl amino propyl trialkoxysilane, and the like.

  Examples of the organosilicon compound having one amino group-protected group include compounds represented by the following formulas, and amino group protecting agents generally used in peptide synthesis reactions and the like are listed above. It can be obtained by reacting with a (dialkoxy) monoalkylsilyl compound and a (trialkoxy) silyl compound.

  Examples of the (dialkoxy) monoalkylsilyl compound or (trialkoxy) silyl compound having an oxirane ring include 2- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, 3-glycidoxypropyltrialkoxysilane, and 3-glycidoxy. And propylmethyl dialkoxysilane.

  As at least one organosilicon compound having a carboxyl group, for example, a compound represented by the following formula (2):

{In the formula, g is an integer of 1 or 2, and when g is 1, Z is a group selected from a divalent aromatic group, an alicyclic group, and an aliphatic group, and g is When 2, Z is a tetravalent aromatic group. G is a divalent organic group containing a carbon atom directly bonded to a silicon atom, and d is an integer of 0 or 1. R ⁴ and R ⁵ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and e is an integer of 0 or 1. R ³ is a hydrogen atom or a monovalent hydrocarbon group. }.
The organosilicon compound can be obtained by reacting a (dialkoxy) monoalkylsilyl compound or (trialkoxy) silyl compound having an amino group with a dicarboxylic acid anhydride or a tetracarboxylic dianhydride and a derivative thereof. it can.

  As dicarboxylic acid anhydride or tetracarboxylic dianhydride, and derivatives thereof, various structures can be used, such as maleic anhydride, phthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 4-methylcyclohexane. -1,2-dicarboxylic anhydride, 1-cyclohexene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, 1,2-naphthalic anhydride, 1,8-naphthal Acid anhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 2, 2-bis (3,4-dicarboxyphenyl) hexafluoroisopropylidenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarbonate Boronic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl Tetracarboxylic dianhydride etc. are mentioned.

  Among these, phthalic anhydride, pyromellitic dianhydride, and 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride are particularly preferable in consideration of the effect of excellent adhesion to the base substrate. .

  In addition, (dialkoxy) monoalkylsilyl compounds or (trialkoxy) silyl compounds having amino groups, which are reacted with dicarboxylic acid anhydrides or tetracarboxylic dianhydrides and their derivatives, and various kinds of compounds including those mentioned above 3-Aminopropyltriethoxysilane is particularly preferred when the structure can be used and the adhesion to the underlying substrate is taken into account.

  Other examples of the (dialkoxy) monoalkylsilyl compound or (trialkoxy) silyl compound having a group capable of reacting with an epoxy resin by heat include N-2 (aminoethyl) -3-aminopropyltrialkoxysilane, N- ( 2-aminoethyl) -3-aminopropylmethyl dialkoxysilane, 3_-trialkoxysilyl-N- (1.3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrialkoxysilane, 3-ureido Propyltrialkoxysilane, 3-ureidopropylmethyldialkoxysilane, 3-mercaptopropyltrialkoxysilane, 3-mercaptopropylmethyldialkoxysilane, bis (trialkoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltria Kokishishiran, 3- (trialkoxysilyl) propyl succinimide anhydride, N- [3- (trialkoxysilyl) propyl] phthalate amidosulfonic acid, and the like.

(C) The organosilicon compound having at least one group capable of reacting with an epoxy resin by heat may be a single compound or a mixture of two or more. (A) The compounding quantity of the organosilicon compound which has at least 1 group which can react with an epoxy resin with the heat | fever with respect to 100 mass parts of polyamide resins is 0.1-25 mass parts, and 0.3-20 mass Part. When the said compounding quantity is 0.1 mass part or more, the improvement effect of the adhesiveness of the photosensitive resin to a base substrate is favorable. Moreover, when the said compounding quantity is 25 mass parts or less, the concern of precipitation by the dark reaction of the organosilicon compounds which have at least one group which can react with an epoxy resin with the heat | fever in the photosensitive resin composition is reduced significantly. To do.

<(D) Other ingredients>
The above-described photosensitive polyamide resin composition is preferably dissolved in a solvent to form a varnish and used as a photosensitive polyamide resin composition solution. As the solvent, a polar organic solvent is preferably used from the viewpoint of solubility in the component (A) polyamide resin and (B) photoinitiator. Specifically, N, N-dimethylformamide, N-methylpyrrolidone (hereinafter also referred to as “NMP”), N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ -Butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, etc. may be mentioned, and these may be used alone or in combination of two or more. Can do.

  These solvents are preferably used in the range of 15 to 750 parts by mass with respect to 100 parts by mass of the (A) polyamide resin, depending on the coating film thickness and viscosity.

  Furthermore, in order to improve the storage stability of the said photosensitive polyamide resin composition, it is preferable that alcohols are included in the organic solvent used as a solvent.

  The alcohol that can be used is not particularly limited as long as it has an alcoholic hydroxyl group in the molecule. Specific examples thereof include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butyl. Lactic acid esters such as alcohol, isobutyl alcohol, tert-butyl alcohol, ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, Propylene glycol monoalkyl ethers such as propylene glycol-1- (n-propyl) ether and propylene glycol-2- (n-propyl) ether, ethylene glycol methyl ether, ethylene glycol Le ethyl ether, mono-alcohols such as ethylene glycol -n- propyl ether, 2-hydroxyisobutyric acid esters, ethylene glycol, and di alcohols such as propylene glycol. Among these, lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyric acid esters, and ethyl alcohol are preferable. Particularly, ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, propylene Glycol-1- (n-propyl) ether is more preferred.

  The alcohol content in the total solvent is preferably 5 to 50% by weight, more preferably 10 to 30% by weight. When the alcohol content is 5% by weight or more, the storage stability of the photosensitive polyamide resin composition is improved. Moreover, when it is 50 weight% or less, the solubility of (A) polyamide resin becomes favorable.

  A sensitizer can also be added to the photosensitive polyamide resin composition of the present invention in order to further improve the photosensitivity. Examples of the sensitizer for improving the photosensitivity include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, 2,6-bis ( 4'-diethylaminobenzal) cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone P-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p -Dimethylaminophenylvinylene) Isonaphthothiazole 1,3-bis (4′-dimethylaminobenzal) acetone, 1,3-bis (4′-diethylaminobenzal) acetone, 3,3′-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl -7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N′-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2- Lucaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethyl) Aminostyryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, benzotriazole, 5-methylbenzotriazole, 5-phenyltetrazole and the like. Among these, it is preferable to use a combination of a compound having a mercapto group and a compound having a dialkylaminophenyl group in terms of photosensitivity. These can be used alone or in combination of 2 to 5 kinds.

  The sensitizer for improving the photosensitivity is preferably used in an amount of 0.05 to 12 parts by mass with respect to 100 parts by mass of the (A) polyamide resin.

  In order to improve the resolution of the relief pattern, a monomer having a photopolymerizable unsaturated bond can be added to the photosensitive polyamide resin composition of the present invention. Such a monomer is preferably a (meth) acryl compound that undergoes a radical polymerization reaction with a photopolymerization initiator, and is not particularly limited to the following, but includes ethylene glycol or polyethylene including diethylene glycol and tetraethylene glycol dimethacrylate. Mono- or diacrylate and methacrylate of glycol, mono- or diacrylate and methacrylate of propylene glycol or polypropylene glycol, mono-, di- or triacrylate and methacrylate of glycerol, cyclohexane diacrylate and dimethacrylate, diacrylate of 1,4-butanediol and Dimethacrylate, 1,6-hexanediol diacrylate and dimethacrylate, neopentyl glycol diacrylate And dimethacrylate, mono or diacrylate and methacrylate of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide or derivatives thereof, methacrylamide or derivatives thereof, trimethylolpropane triacrylate and methacrylate, di or glycerol Mention may be made of compounds such as triacrylates and methacrylates, di, tri or tetra acrylates and methacrylates of pentaerythritol, or ethylene oxide or propylene oxide adducts of these compounds.

It is preferable that 1-40 mass parts is used for the monomer which has a photopolymerizable unsaturated bond for improving the resolution of a relief pattern with respect to 100 mass parts of (A) polyamide resin.
The photosensitive polyamide resin composition of the present invention can further contain a thermally crosslinkable compound in order to improve film properties (particularly heat resistance) after heat curing. The thermally crosslinkable compound is (A) a compound that thermally crosslinks the polyamide resin, or a compound that itself forms a thermally crosslinked network. As the thermally crosslinkable compound, a compound having an alkoxymethyl group as a thermally crosslinkable group, for example, an amino resin or a derivative thereof is preferably used. Of these, urea resins, glycol urea resins, hydroxyethylene urea resins, melamine resins, benzoguanamine resins, and derivatives thereof are preferably used. Particularly preferred is hexamethoxymethylated melamine.

  (A) It is preferable that the compounding quantity of the heat crosslinkable compound with respect to 100 mass parts of polyamide resins is 1-40 mass parts, and it is more preferable that it is 3-15 mass parts. When the said compounding quantity is 1 mass part or more, the film | membrane characteristic after heat-hardening of the photosensitive polyamide resin composition of this invention can be improved further. Moreover, when the said compounding quantity is 40 mass parts or less, the residual monomer component used as the degassing component from a cured film can be suppressed also in low temperature hardening.

  In addition, a thermal polymerization inhibitor may be added to the photosensitive polyamide resin composition of the present invention in order to improve the viscosity of the composition solution during storage and the stability of photosensitivity. Examples of thermal polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6 -Di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N- Sulfopropylamino) phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt and the like are used.

  The amount of the thermal polymerization inhibitor added to the photosensitive polyamide resin composition is preferably in the range of 0.005 to 6 parts by mass with respect to 100 parts by mass of the (A) polyamide resin.

  In the photosensitive polyamide resin composition of the present invention, an organic titanium compound can be used as a component for improving heat resistance and chemical resistance. The usable organic titanium compound is not particularly limited as long as the organic chemical substance is bonded to the titanium atom via a covalent bond or an ionic bond.

  Specific examples of the organic titanium compound include titanocenes. As the titanocene, pentamethylcyclopentadienyl titanium trimethoxide and the like are used. In this case, if titanocenes that function as a photoinitiator such as bis (2,6-difluoro-3- (1-hydropyrrol-1-yl) phenyl) titanocene are used, there are other cases that may be used in the present invention. In some cases, it is difficult to obtain a good pattern due to interference with the photoinitiator. As the organic titanium compound to be used, an organic titanium compound that does not function as a photoinitiator is more preferable.

  Another specific example of the organic titanium compound that can be used in the present invention is a titanium chelate. In the present invention, among titanium chelates, those having two or more alkoxy groups are more preferred because of the stability of the composition and good pattern, and specific preferred examples include titanium bis (triethanol Amine) diisopropoxide, titanium di (n-butoxide) (bis-2,4-pentanedionate), titanium diisopropoxide (bis-2,4-pentanedionate), titanium diisopropoxide bis ( Tetramethylheptanedionate), titanium diisopropoxide bis (ethylacetoacetate) and the like.

  Also, titanium tetra (n-butoxide), titanium tetraethoxide, titanium tetra (2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide Tetraalkoxides such as titanium tetramethylphenoxide, titanium tetra (n-nonyloxide), titanium tetra (n-propoxide), titanium tetrastearyloxide, titanium tetrakis (bis-2,2- (allyloxymethyl) butoxide), Monoalkoxides such as titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzenesulfonate) isopropoxide, Titanium oxides such as nium oxide bis (pentanedionate), titanium oxide bis (tetramethylheptanedionate), phthalocyanine titanium oxide, tetraacetylacetonates such as titanium tetraacetylacetonate, isopropyltridodecylbenzenesulfonyl titanate, etc. Titanate coupling agents can also be used.

  The addition amount of these organic titanium compounds is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the (A) polyamide resin. When the addition amount is 0.1 parts by mass or more, desired heat resistance and chemical resistance are exhibited, and when it is 10 parts by mass or less, the storage stability is excellent.

  In addition to the above, the photosensitive polyamide resin composition of the present invention does not inhibit various characteristics of the photosensitive polyamide resin composition of the present invention, including a scattered light absorber and a coating film smoothness imparting agent. As long as necessary, various additives can be appropriately blended.

<Curing relief pattern and semiconductor device manufacturing method>
As one aspect of the method of forming the cured relief pattern which consists of photosensitive polyimide resin using the photosensitive polyamide resin composition of this invention, the following processes are included:
(A) a step of applying a photosensitive polyamide resin composition or a photosensitive polyamide resin composition solution on a substrate to form a coating film; the coating film may be dried after application, if necessary;
(B) exposing the coating film directly or through a patterning mask; irradiating the coating film with ultraviolet rays through a photomask or reticle having a pattern, or directly;
(C) A step of developing the coating film using a developing solution; by developing with the developing solution, the unexposed portion of the coating film is removed with a solvent, thereby forming a relief pattern on the substrate. Process,
(D) Heat curing step: A step of imidizing the polyamic acid ester in the relief pattern by heat curing the resulting relief pattern, thereby forming a cured relief pattern made of a polyimide resin on the substrate is preferred.

  Examples of the substrate that can be used in the method of forming a cured relief pattern include a silicon wafer, metal, glass, semiconductor, metal oxide insulating film, silicon nitride, and the like, and a silicon wafer is preferably used.

  As a method for coating the photosensitive polyamide resin composition used in the present invention on a substrate, methods conventionally used for coating photosensitive polyamide resin compositions, such as spin coaters, bar coaters, blade coaters, A method of applying with a curtain coater, a screen printer, or the like, a method of spraying with a spray coater, or the like can be used.

  As a method for drying the coating film, methods such as air drying, heat drying with an oven or hot plate, and vacuum drying are used. More specifically, when air drying or heat drying is performed, it can be performed at 20 ° C. to 140 ° C. for 1 minute to 1 hour. Hereinafter, this process is also referred to as pre-baking.

  The coating film thus obtained is exposed with an ultraviolet light source or the like through a photomask or reticle having a pattern using an exposure apparatus such as a contact aligner, a mirror projection, or a stepper.

  Thereafter, post-exposure baking (PEB) or a pre-development baking by any combination of temperature and time may be performed as necessary for the purpose of improving the photosensitivity. The range of the baking conditions is preferably a temperature of 40 to 120 ° C. and a time of 10 seconds to 240 seconds, but is not limited to this range as long as the various properties of the photosensitive polyamide resin composition of the present invention are not impaired.

  The developer used for development is preferably a good solvent for the photosensitive polyamide resin composition or a combination of the good solvent and the poor solvent. As the good solvent, N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, and the like are preferable. Toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water and the like are used. When a good solvent and a poor solvent are mixed and used, the ratio of the poor solvent to the good solvent is adjusted depending on the solubility of the polymer. Moreover, several types of solvents can be used in combination.

  Further, as a developer used for development, for example, when an aromatic bisaminophenol is used as all or part of a diamine compound having a divalent or tetravalent organic group Y used in the polyamide resin of the present invention, An alkaline aqueous solution can also be used. Examples of alkaline aqueous solutions include aqueous solutions of inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia, aqueous solutions of organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, tetramethylammonium hydroxide, and tetrabutyl. An aqueous solution of a quaternary ammonium salt such as ammonium hydroxide or the like, and an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like, as necessary, can be used.

  As a developing method, an arbitrary method can be selected and used from conventionally known photoresist developing methods such as a rotary spray method, a paddle method, and an immersion method involving ultrasonic treatment.

  Further, after development, for the purpose of adjusting the shape of the relief pattern, post-development baking at any combination of temperature and time may be performed as necessary.

  The polyamide resin pattern obtained as described above is a cured relief pattern made of a polyamide (imide) resin having excellent heat resistance and chemical resistance by heating to dilute the solvent and advance the crosslinking reaction. Convert to Various methods such as a method using a hot plate, a method using an oven, and a method using a temperature rising oven capable of setting a temperature program can be selected as the method for heat curing. Heating can be performed at 150 ° C. to 400 ° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas for heat curing, and an inert gas such as nitrogen or argon may be used.

  Hereinafter, the present invention will be described with reference to examples and comparative examples. In addition, Table 1 below shows a list of combinations of polymer raw materials of the following synthesis examples.

[Synthesis Example 1]
(Synthesis of Phthalic Acid Compound Encapsulated AIPA-MO)
In a separable flask having a capacity of 5 liters, 543.5 g (3.0 mol) of 5-aminoisophthalic acid (hereinafter abbreviated as AIPA) and 1700 g of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were charged. The mixture was stirred and heated to 50 ° C. in a water bath. To this, 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate diluted with 500 g of gamma-butyrolactone (hereinafter referred to as GBL) was added dropwise with a dropping funnel, and stirred at 50 ° C. for about 2 hours. .

  After the completion of the reaction (disappearance of 5-aminoisophthalic acid) was confirmed by low molecular weight gel permeation chromatography (hereinafter referred to as low molecular weight GPC), the reaction solution was poured into 15 liters of ion-exchanged water, stirred, Let stand, wait for crystallization and precipitation of the reaction product, filter and wash with water, and then vacuum-dry at 40 ° C. for 48 hours to give an amino group of 5-aminoisophthalic acid and 2-methacryloyloxyethyl isocyanate. AIPA-MO in which an isocyanate group acted was obtained. The obtained AIPA-MO had a low molecular weight GPC purity of almost 100%.

[Synthesis Example 2]
(Synthesis of polyamide P-1)
In a 2 L separable flask, 75.03 g (0.255 mol) of biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride (hereinafter referred to as BPDA) and 2-hydroxyethyl methacrylate were added. 66.37 g (0.51 mol), 40.34 g (0.51 mol) of pyridine, and 200 g of GBL were added, mixed, stirred for 4 hours while heating at 40 ° C., and then stirred at room temperature for 16 hours. To this, 15.13 g (0.045 mol) of AIPA-MO obtained in Synthesis Example 1, 10.68 g (0.135 mol) of pyridine, and 100 g of GBL were added and mixed, and cooled to 5 ° C. in an ice bath. . A solution obtained by dissolving and diluting 123.80 g (0.60 mol) of N, N-dicyclohexylcarbodiimide (hereinafter referred to as DCC) in 125 g of GBL was added dropwise thereto over about 20 minutes under ice cooling. A solution obtained by dispersing 56.07 g (0.28 mol) of 4′-diaminodiphenyl ether (hereinafter referred to as DDE) in 170 g of GBL was added dropwise over about 20 minutes, and the temperature was kept below 5 ° C. in an ice bath for 3 hours. The ice bath was then removed and the mixture was stirred at room temperature for 5 hours.

  Thereafter, dicyclohexylurea (hereinafter referred to as DCU) derived from the dehydration condensing agent, which was precipitated in the polycondensation process, was filtered off under pressure, and 2000 g of ethanol was added dropwise while stirring the filtrate (polymer solution). The polymer was separated and redissolved in 650 g NMP. This redissolved solution was added dropwise with stirring of 7 liters of ion-exchanged water to disperse and precipitate the polymer, and after recovery and washing, vacuum drying was performed at 40 ° C. for 48 hours to obtain polyamide P-1. The polystyrene-equivalent GPC weight average molecular weight (column: Shodex KD-806M × 2, NMP flow rate: 1.0 ml / min) measured using NMP as an eluent was 32,000.

[Synthesis Example 3]
(Synthesis of polyamide P-2)
Into a separable flask having a capacity of 2 liters, 100.89 g (0.3 mol) of AIPA-MO obtained in Synthesis Example 1, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were added and mixed, and then mixed in an ice bath. At 5 ° C. A solution obtained by dissolving and diluting 125.0 g (0.606 mol) of DCC in 125 g of GBL was added dropwise over about 20 minutes under ice cooling, followed by 4,4′-bis (4-aminophenoxy) biphenyl (hereinafter, BAPB) 103.16 g (0.28 mol) dissolved in 168 g of NMP was added dropwise over about 20 minutes, maintained for 3 hours in an ice bath at less than 5 ° C., then removed from the ice bath at room temperature. For 5 hours.

  Thereafter, the DCU derived from the dehydration condensing agent that was precipitated in the polycondensation process was filtered off under pressure, and while stirring the filtrate (polymer solution), a mixed solution of 840 g of water and 560 g of isopropanol was added dropwise, and the precipitated polymer was obtained. Separated and redissolved in 650 g NMP. This re-dissolved solution was added dropwise with stirring of 5 liters of ion-exchanged water to disperse and precipitate the polymer, recovered, washed with water, and then vacuum-dried at 40 ° C. for 48 hours to obtain polyamide P-2. The polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 3 was 34,700.

[Synthesis Example 4]
(Synthesis of polyamide P-3)
In a 5 L separable flask, 310.22 g (1.00 mol) of diphenyl ether-3,3 ′, 4,4′-tetracarboxylic dianhydride and 270.69 g (2.08 mol) of 2-hydroxyethyl methacrylate , 158.2 g (2.00 mol) of pyridine and 1000 g of GBL were added, mixed, and stirred at room temperature for 16 hours. A solution obtained by dissolving and diluting 400.28 g (1.94 mol) of DCC in 400 g of GBL was added dropwise over about 30 minutes under ice cooling, and then 185.97 g (0.93 mol) of DDE was dispersed in 650 g of GBL. Over 60 minutes. The mixture was stirred for 3 hours while being ice-cooled, then the ice-cooled bath was removed, and the mixture was further stirred for 1 hour. After the DCU precipitated in the polycondensation process is filtered off under pressure, the reaction solution is dropped into 40 L of ethanol, the polymer precipitated at that time is separated, washed, and vacuum dried at 50 ° C. for 24 hours, Polyamide P-3 was obtained. The polystyrene-equivalent GPC weight average molecular weight measured under the same conditions as in Synthesis Example 3 was 29,000.

[Synthesis Example 5]
(Synthesis of organosilicon compound S-1)
Pyromellitic anhydride 21.8 g (0.1 mol) and NMP 164 g were charged into a 500 mL round bottom flask, and stirring was started. While this solution was cooled to 0 ° C. and maintained, a solution prepared by diluting 44.2 g (0.2 mol) of 3-aminopropyltriethoxysilane with 100 g of NMP was added dropwise. After completion of dropping, the solution is returned to room temperature and stirred for 4 hours, whereby the acid anhydride group of pyromellitic anhydride and the amino group of 3-aminopropyltriethoxysilane react to form a half acid / half amidated organic compound. A 20 mass% NMP solution of silicon compound S-1 was obtained.

[Example 1]
100 g of the polyamide (P-1) obtained in Synthesis Example 2 was added to 5 g of 1,3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime (photoinitiator), 8 g of tetraethylene glycol dimethacrylate, 1-phenyl. -5-mercaptotetrazole 2 g, hexamethoxymethylmelamine (C-1) 4 g, N-phenyldiethanolamine 10 g, organosilicon compound (S-1) 3 g obtained in Synthesis Example 5, and 2-nitroso-1-naphtho Along with 0.02 g of potassium, it was dissolved in a mixed solvent consisting of 160 g of NMP and 40 g of ethyl lactate. The viscosity of the obtained solution was adjusted to about 20 poises by further adding a small amount of the above mixed solvent to obtain photosensitive polyamide resin composition V-1.

[Example 2]
A photosensitive polyamide resin composition was used in the same manner as in Example 1 except that 3-glycidoxypropyltrimethoxysilane (S-2, trade name KBM-403) was used instead of S-1. V-2.

[Example 3]
In the same manner as in Example 1, except that 3-aminopropyltrimethoxysilane (S-3, manufactured by Momentive Performance Materials Japan GK, trade name TSL-8331E) was used instead of S-1. It was set as photosensitive polyamide resin composition V-3.

[Example 4]
A photosensitive polyamide resin composition V-4 was prepared in the same manner as in Example 1 except that the polyamide resin (P-2) obtained in Synthesis Example 3 was used in place of P-1.

[Comparative Example 1]
A photosensitive polyamide resin composition V-5 was obtained in the same manner as in Example 1 except that the polyamide resin (P-3) obtained in Synthesis Example 4 was used instead of P-1.

[Comparative Example 2]
A photosensitive polyamide resin composition V-6 was prepared in the same manner as in Example 1 except that S-1 was changed to 0 g.

[Comparative Example 3]
Photosensitive polyamide resin composition V- was replaced with P-1 in the same manner as in Example 1 except that the polyamide resin (P-2) obtained in Synthesis Example 4 was used and S-1 was changed to 0 g. It was set to 7.

[Comparative Example 4]
Photosensitive polyamide resin composition V was obtained in the same manner as in Example 1 except that 3-methacryloyloxypropyltriethoxysilane (S-4, manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-503) was used instead of S-1. It was set to -8.

<(1) Evaluation of resist stripping solution resistance>
The resin composition solutions of Examples 1 to 4 and Comparative Examples 1 to 4 were applied onto a 6-inch silicon wafer using a spin coater (manufactured by Tokyo Electron, model name: Clean Track Mark 8). Pre-baking was performed for a minute to obtain a coating film having an initial film thickness of 8 microns. The coatings, ghi-line stepper exposing machine (UT manufactured, model name Prisma) by, through evaluation photomask, exposure 50 mJ / cm ² by stepwise varied in the range of 100~1100mJ / cm ² and exposure did. The obtained relief pattern film was subjected to heat curing treatment at 350 ° C. for 2 hours in a nitrogen atmosphere using a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B) to prepare a cured relief pattern film.

  These cured films are immersed in a resist stripping solution (mixture of potassium hydroxide, dimethyl sulfoxide, 3-methoxy-3-methylbutanol in a weight ratio of 1:59:40) heated to 100 ° C. for 1 hour, and then allowed to cool. After washing with running water for 1 minute and drying, the surface pattern was observed under an optical microscope. Change in film thickness due to pattern swelling / dissolution (unit%. 100% is no film thickness change. 100% or more swells, less than 100% film dissolves.) did. The results are shown in Table 2 below.

<(2) Evaluation of reflow resistance>
(1) The cured relief pattern prepared in the same manner as in the evaluation of resist stripping solution resistance is treated with a mixed solution of potassium hydroxide / dimethyl sulfoxide (DMSO) / 3-methoxy-3-methylbutanol in the same manner. Subsequently, paste flux (trade name WS600MHV manufactured by Cookson Electronics Co., Ltd.) was applied onto the pattern, and this was used using a mesh belt type continuous firing furnace (model name 810-2-5Z manufactured by Koyo Thermo Systems Co., Ltd.). It was heated to a peak temperature of 260 ° C. under a nitrogen atmosphere under simulated solder reflow conditions. This is in conformity with the solder reflow conditions described in Section 7.6 of IPC / JEDEC J-STD-020A, which is a standard of the US semiconductor industry association regarding the evaluation method of semiconductor devices, and the solder melting point is set to a high temperature of 220 ° C. Assumed and normalized.

  The film after the simulated reflow treatment was immersed in pure water for 1 hour to remove the flux and dried, and then the surface pattern was observed under an optical microscope. Change in film thickness due to pattern swelling / dissolution (unit%. 100% is no film thickness change. 100% or more swells, less than 100% film dissolves.) did. The results are shown in Table 2 below.

<(3) Evaluation of adhesion to underfill layer>
The resin composition solutions of Examples 1 to 4 and Comparative Examples 1 to 4 were applied onto a 6-inch silicon wafer using a spin coater (manufactured by Tokyo Electron, model name: Clean Track Mark 8). Pre-baking was performed for a minute to obtain a coating film having an initial film thickness of 8 microns. The coatings, ghi-line stepper exposing machine (UT manufactured, model name Prisma) by, through overall exposure photomask for evaluation was 50 mJ / cm ² exposure at an exposure amount 1000 mJ / cm ^2. The obtained coating film was heat-cured for 2 hours at 350 ° C. in a nitrogen atmosphere using a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B) to prepare a cured film without a pattern.

  This cured film was subjected to a plasma treatment for 10 minutes using a plasma cleaning device (EXAM type manufactured by Shinko Seiki Co., Ltd.) under the conditions of a flow rate of 46 ml / min, an internal pressure of 50 Pa, a soft mode, and 133 W. The resist stripper treatment was performed by the method (1), and the simulated reflow condition treatment was performed by the method (2). From this wafer with a cured film, 5 mm square and 2 cm square wafer pieces were cut out using a dicing saw (DAD-2H / 6T manufactured by DISCO Corporation). Using a polyimide tape having a thickness of 60 μm as a guide, 0.5 mg of an underfill material (U8439-1 manufactured by NAMICS) was applied in a circle between a 2 cm square sample piece and a 5 mm square sample piece, and 100 ° C. 1 on a hot plate. After pre-baking for a minute, a sample piece was prepared by performing heat curing in an oven at 150 ° C. for 60 minutes. The created sample was subjected to a reflow treatment after heating and humidification under the conditions specified by JEDEC Moisture Sensitivity Level 3 using a constant temperature and humidity chamber (PR-2KT manufactured by Espec Corp.) and the mesh belt type continuous firing furnace. The bond strength between the cured film and the underfill layer was measured by shear fracture using a bond tester (series 4000 manufactured by Dage) while the sample was heated to 260 ° C. with a hot plate, and the following criteria were used using an optical microscope. The failure mode was evaluated. The fracture mode was determined to be “◯” when the underfill material was cohesive failure, and “×” was determined as the interface failure between the cured film and the underfill material. The results are shown in Table 2.

<(4) Evaluation of adhesion to silicon substrate>
The resin composition solutions of Examples 1 to 4 and Comparative Examples 1 to 4 were applied onto a 6-inch silicon wafer using a spin coater (manufactured by Tokyo Electron, model name: Clean Track Mark 8). Pre-baking was performed for a minute to obtain a coating film having an initial film thickness of 8 microns. The coatings, ghi-line stepper exposing machine (UT manufactured, model name Prisma) by, through overall exposure photomask for evaluation was 50 mJ / cm ² exposure at an exposure amount 1000 mJ / cm ^2. The obtained coating film was heat-cured for 2 hours at 350 ° C. in a nitrogen atmosphere using a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B) to prepare a cured film without a pattern.

  This cured film was treated with a pressure cooker (121 ° C., 2.0 atm) for 100 hours (PCT-treated sample) in a cross-cut test (JIS K5400) so that 100 squares of 1 mm square could be made. By scratching with a cutter knife, attaching cellophane (registered trademark) tape from above, peeling off, and counting the number of squares remaining on the silicon wafer without adhering to the cellophane (registered trademark) tape, cured film The base silicon adhesion was evaluated. The case where 100 squares remained on the wafer was judged as “◯”, and the others were judged as “x”. The results are shown in Table 2.

  In addition, there is no pattern deformation or film thickness increase / decrease in the results of the resist stripping solution resistance test and the reflow resistance test, and the comprehensive judgment is performed on the adhesion test with the underfill layer and the silicon substrate. Those that did not cause interfacial peeling with each layer in the adhesion test were evaluated as “◯”.

  In Examples 1 to 4, it was shown that good adhesion to the underfill layer was achieved as a result of less damage during resist stripping and reflow. A photosensitive resin composition suitable for producing an area array type semiconductor element package can be provided.

  On the other hand, Comparative Example 1 is a case where a polyamide resin that is not copolymerized with AIPA-MO is used as a raw material, but the chemical resistance is inferior to that of the Examples, and the adhesion to the underfill layer is low. . It is considered that a damaged layer is present at the interface with the underfill layer, leading to deterioration in adhesion.

  Comparative Example 1 is a case in which Comparative Example 1 uses a polyamide resin not copolymerized with AIPA-MO as a raw material and an organosilicon compound suitable for the present invention is added, but the adhesion to the underfill layer is insufficient. It is.

  Comparative Examples 2 and 3 are cases where the preferred organosilicon compound of the present invention was not added to the polyamide resin composition copolymerized with AIPA-MO, but the adhesion to the silicon substrate after PCT treatment was poor.

  Comparative Example 4 is a case where an organosilicon compound different from the preferred organosilicon compound of the present invention was added to the polyamide resin composition copolymerized with AIPA-MO, but the adhesion to the underfill layer was inferior to the examples. It became.

  In summary, the specific polyamide resin shown in the present invention has a tendency to improve the chemical resistance and adhesion with the underfill agent by containing the AIPA-derived structure. When not combined with a silicon compound, the adhesion with the underfill agent is insufficient. In addition, the specific organosilicon compound shown in the present invention does not show the effect of improving the adhesion with the underfill layer in combination with the polyamide resin not containing AIPA-MO. That is, it can be seen that a photosensitive resin composition having excellent underfill adhesiveness and adhesiveness to a silicon substrate cannot be provided except for the combination of the specific polyamide resin and the specific organosilicon compound shown in the present invention.

  As described above, by combining a specific polyamide resin and a specific organosilicon compound shown in the present invention into a photosensitive resin composition, desired photosensitivity with an underfill layer and a semiconductor element chip can be obtained. It was shown that a functional resin composition can be provided.

  The photosensitive resin composition of the present invention includes a semiconductor device surface protective film, an interlayer insulating film, a rewiring insulating film, a flip chip device protective film or a protective film for a device having a bump structure, a multilayer circuit interlayer insulating, a flexible It can be suitably used for applications such as a copper clad cover coat, a solder resist film, or a liquid crystal alignment film.

Claims (7)

(A) The following general formula (1):

{In the formula, X ¹ is a trivalent organic group having 6 to 15 carbon atoms, k is 0 or 2, and Y is a divalent organic group having 6 to 35 carbon atoms when k = 0. Yes, when k = 2, it is a tetravalent organic group having 6 to 35 carbon atoms, X ² is a tetravalent organic group having 6 to 35 carbon atoms, and X ³ is a carbon number having 6 to 15 carbon atoms. It is a divalent organic group, which may be the same or different, l, m and n are integers, have a relationship of 0.05 ≦ l / (l + m + n) ≦ 1, and (l + m + n) is R is an integer of ^{2 to} 150, and R ¹ and R ² are aliphatic groups having at least one radical-polymerizable unsaturated bond group having 5 to 20 carbon atoms, which may contain atoms other than carbon. , May be the same or different. } 100 parts by mass of a polyamide resin including a repeating unit represented by: (B) 0.5 to 20 parts by mass of a photoinitiator; and (C) an organosilicon having at least one group capable of reacting with an epoxy resin by heat. A photosensitive polyamide resin composition comprising 0.1 to 25 parts by mass of a compound. The organic groups X ¹ , X ² , X ³ , and Y in the formula (1) are each independently an aromatic group, an alicyclic group, an aliphatic group, a siloxane group, or a group having a composite structure thereof. The photosensitive polyamide resin composition according to claim 1, wherein the photosensitive polyamide resin composition is a group selected from the above.   (C) the organosilicon compound having at least one group capable of reacting with an epoxy resin by heat is a group selected from the group consisting of a carboxyl group, a carboxylic anhydride group, a sulfonyl group, an oxirane group and an amino group, or The photosensitive polyamide resin composition according to claim 1, wherein the photosensitive polyamide resin composition is an organosilicon compound having at least one group protected. (C) An organosilicon compound having at least one group capable of reacting with an epoxy resin by heat is represented by the following general formula (2):

{In the formula, g is an integer of 1 or 2, Z is a group selected from a divalent aromatic group, an alicyclic group, and an aliphatic group when g is 1, and g is When it is 2, it is a tetravalent aromatic group. G is a divalent organic group containing a carbon atom directly bonded to a silicon atom, and d is an integer of 0 or 1. R ⁴ and R ⁵ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms, and e is an integer of 0 or 1. R ³ is a hydrogen atom or a monovalent hydrocarbon group. } The photosensitive polyamide resin composition of Claim 1 or 2 characterized by the above-mentioned.   The photosensitive polyamide resin composition solution formed by dissolving the photosensitive polyamide resin composition as described in any one of Claims 1-4 in a solvent.   A coating film is formed by applying the photosensitive polyamide resin composition according to any one of claims 1 to 4 or the photosensitive polyamide resin composition solution according to claim 5 on a substrate, and the coating film The film is exposed directly or through a patterning mask, the coating film is developed using a developer, and then heat-cured to form a cured relief pattern.   A semiconductor device having a cured relief pattern obtained by the method according to claim 6.