WO2009151012A1 - Polyamide resin, photosensitive resin composition, method for forming cured relief pattern, and semiconductor device - Google Patents

Abstract

Disclosed is a photosensitive resin composition having excellent photosensitive characteristics, which provides a resin film with excellent film characteristics even when the resin film is formed under heating/curing conditions such as at 200°C or less.  A polyamide resin used in the photosensitive resin composition is also disclosed.  The polyamide resin contains structural units represented by formula (1) with a repetition number of 2-150 which is within the range of 80-100% of the total number of the structural units constituting the polyamide resin. [In formula (1), X represents a trivalent organic group having 6-15 carbon atoms; m represents 0 or 2; Y represents a divalent organic group having 6-35 carbon atoms when m = 0, and represents a tetravalent organic group having 6-35 carbon atoms when m = 2; and R1 represents an aliphatic group having at least one radically polymerizable unsaturated linking group with 5-20 carbon atoms, which may contain an atom other than carbon atoms.]

Description

Polyamide resin, photosensitive resin composition, method for forming cured relief pattern, and semiconductor device

The present invention relates to a polyamide that can be used for an insulating material for electronic parts, a surface protective film for semiconductor devices, an interlayer insulating film, a heat-resistant coating film such as an alpha ray shielding film, and a semiconductor device equipped with an image sensor, micromachine, or microactuator. The present invention relates to a resin, a photosensitive resin composition containing the polyamide resin, a method for forming a cured relief pattern using the photosensitive resin composition, and a semiconductor device having the cured relief pattern. More specifically, the present invention is a novel photosensitivity that exhibits excellent photosensitivity during ultraviolet exposure, such as excellent heat resistance, chemical resistance, mechanical properties, and low residual stress characteristics even under heat curing conditions of 200 ° C. or lower. The present invention relates to a polyamide resin, a photosensitive resin composition containing the polyamide resin, and a semiconductor device manufactured using the photosensitive resin composition.

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. . This resin is usually provided in the form of a photosensitive polyimide precursor composition, which is applied to a substrate, irradiated with an actinic ray (exposure) through a desired patterning mask, developed, and heat-cured (heat By performing the (imidization) treatment, a relief pattern made of a heat-resistant polyimide resin can be easily formed (see, for example, Patent Document 1 below).

In recent years, in the manufacturing process of a semiconductor device, mainly due to the material and structural design of constituent members, there is an increasing demand for a material capable of performing heat curing (thermal imidization) treatment at a lower temperature. In the case of the polyimide resin precursor composition of the prior art, if the heat curing treatment temperature is lowered, the thermal imidation cannot be completed and various physical properties deteriorate, so the lower limit of the heat curing treatment temperature is about 300 ° C. at most. .

Although efforts have been made to reduce the heat-curing temperature by devising the polymer skeleton structure and composition additives, about 250 ° C. is considered the limit to maintain the practical polyimide film characteristics (for example, the following patent documents) 2).

Therefore, a photosensitive resin composition that is excellent in photosensitive characteristics during ultraviolet exposure and exhibits film characteristics suitable for practical use even under heat curing conditions of 200 ° C. or less has not been known in the art.

JP-A-6-342211 JP 2003-316002 A JP-A-63-182322 International Publication No. 2006/008991 Pamphlet

Patent Document 3 discloses a polyamide in which a photosensitive group is directly bonded to a resin skeleton via an amide group, and Patent Document 4 discloses a polyimide amide. When the (thermal imidation) treatment was performed at a lower temperature, it was not suitable for practical use. The problems to be solved by the present invention are excellent in sensitivity and resolution. For example, even when a resin film is formed under a low-temperature heat-curing condition such as 200 ° C. or less, film characteristics excellent in chemical resistance are imparted to the resin film. It is to provide a polyamide resin and a photosensitive resin composition. 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 studies to solve the above problems, the present inventors have found that the above problems can be solved by producing a photosensitive resin composition based on a polyamide produced from a specific raw material. The invention has been completed. Specifically, the present invention is as follows [1] to [16]:

｛式中、Ｘは炭素数が６～１５の３価の有機基であり、ｍは０又は２であり、Ｙは、ｍ＝０のとき炭素数が６～３５の２価の有機基、ｍ＝２のとき炭素数が６～３５の４価の有機基であり、Ｒ₁は炭素以外の原子を含んでいてもよい、炭素数が５～２０のラジカル重合性の不飽和結合基を少なくとも１つ有する脂肪族基である。｝で表される構成単位を、繰り返し数２～１５０の範囲内でかつ該繰り返し数がポリアミド樹脂を構成する全構成単位の総数の８０～１００％の範囲内となるように含む、ポリアミド樹脂。 [1] The following formula (1):

{Wherein X is a trivalent organic group having 6 to 15 carbon atoms, m is 0 or 2, and Y is a divalent organic group having 6 to 35 carbon atoms when m = 0, When m = 2, it is a tetravalent organic group having 6 to 35 carbon atoms, and R ₁ is a radically polymerizable unsaturated bond group having 5 to 20 carbon atoms, which may contain atoms other than carbon. It is an aliphatic group having at least one. Are included so that the number of repetitions is in the range of 2 to 150 and the number of repetitions is in the range of 80 to 100% of the total number of all the structural units constituting the polyamide resin.

｛式中、Ｘは炭素数が６～１５の３価の有機基であり、ｍは０又は２であり、Ｙは、ｍ＝０のとき炭素数が６～３５の２価の有機基、ｍ＝２のとき炭素数が６～３５の４価の有機基であり、Ｗは炭素数が６～１５の２価の有機基であり、ｋは１以上の整数であり、同時に（ｎ＋ｋ）は５～１５０の整数であり、Ｒ₁は炭素以外の原子を含んでいてもよい、ラジカル重合性の不飽和結合基を少なくとも１つ有する炭素数が５～２０の脂肪族基である。｝で表される構造を、上記式（２）中の繰り返し数ｎがポリアミド樹脂を構成する全構成単位の総数の８０％以上となるように含む、ポリアミド樹脂。 [2] The following formula (2):

{Wherein X is a trivalent organic group having 6 to 15 carbon atoms, m is 0 or 2, and Y is a divalent organic group having 6 to 35 carbon atoms when m = 0, When m = 2, it is a tetravalent organic group having 6 to 35 carbon atoms, W is a divalent organic group having 6 to 15 carbon atoms, k is an integer of 1 or more, and (n + k) Is an integer of 5 to 150, and R ₁ is an aliphatic group having 5 to 20 carbon atoms which may contain atoms other than carbon and has at least one radical-polymerizable unsaturated bond group. } The polyamide resin containing the structure represented by the formula (2) so that the repeating number n in the formula (2) is 80% or more of the total number of all the structural units constituting the polyamide resin.

｛式中、Ｘは炭素数が６～１５の３価の有機基であり、ｍは０又は２であり、Ｙは、ｍ＝０のとき炭素数が６～３５の２価の有機基、ｍ＝２のとき炭素数が６～３５の４価の有機基であり、Ｗは炭素数が６～１５の２価の有機基であり、ｌは０または１以上の整数であり、同時に（ｎ＋ｌ）は２～１５０の整数であり、Ｒ₁は炭素以外の原子を含んでいてもよい、ラジカル重合性の不飽和結合基を少なくとも１つ有する炭素数が５～２０の脂肪族基である。｝で表される構造のみを構成単位とし、上記式（３）中の繰り返し数ｎがポリアミド樹脂を構成する全構成単位の総数の８０～１００％の範囲内であるポリアミド樹脂。 [3] The following formula (3):

{Wherein X is a trivalent organic group having 6 to 15 carbon atoms, m is 0 or 2, and Y is a divalent organic group having 6 to 35 carbon atoms when m = 0, When m = 2, it is a tetravalent organic group having 6 to 35 carbon atoms, W is a divalent organic group having 6 to 15 carbon atoms, l is 0 or an integer of 1 or more, and ( n + 1) is an integer of 2 to 150, and R ₁ is an aliphatic group having 5 to 20 carbon atoms which may contain atoms other than carbon and which has at least one radical-polymerizable unsaturated bond group. . }, A polyamide resin in which the repeating unit n in the formula (3) is in the range of 80 to 100% of the total number of all the structural units constituting the polyamide resin.

｛式中、Ｒ₂はラジカル重合性の不飽和結合基を少なくとも１つ有する炭素数４～１９の脂肪族基である。｝で表される基である、上記［１］～［３］のいずれかに記載のポリアミド樹脂。 [4] The above R ₁ is represented by the following formula (4):

{In the formula, R ₂ is a C 4-19 aliphatic group having at least one radical-polymerizable unsaturated bond group. }, The polyamide resin according to any one of [1] to [3] above.

[5] The polyamide resin according to any one of [1] to [3], wherein R ₁ is a group having at least one (meth) acryloyloxymethyl group.

[6] The above W, X, and Y are each independently a group selected from the group consisting of an aromatic group, an alicyclic group, an aliphatic group, a siloxane group, and a group of a composite structure thereof. [1] The polyamide resin according to any one of [3].

[7] A photosensitive resin composition comprising (A) 100 parts by mass of the polyamide resin according to any one of [1] to [6], and (B) 0.5 to 20 parts by mass of a photopolymerization initiator.

[8] The photosensitivity according to [7], further including (C) a monomer having a photopolymerizable unsaturated bond group in an amount of 1 to 40 parts by mass with respect to 100 parts by mass of the polyamide resin of (A). Resin composition.

[9] (D) A heat-crosslinkable compound is further contained in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the polyamide resin (A), and the (D) heat-crosslinkable compound is a polyamide (A) The photosensitive resin composition according to the above [7] or [8], which is a compound that thermally cross-links a resin or a compound that itself forms a heat-crosslinking network.

[10] The photosensitive resin composition according to [9] above, wherein the (D) thermally crosslinkable compound has an alkoxymethyl group as a thermally crosslinkable group.

[11] The method according to any one of [7] to [10], further including (E) a silane coupling agent in an amount of 0.1 to 25 parts by mass with respect to 100 parts by mass of the polyamide resin of (A). Photosensitive resin composition.

[12] The photosensitive resin composition according to the above [11], wherein the (E) silane coupling agent is an organosilicon compound having a (dialkoxy) monoalkylsilyl group or a (trialkoxy) silyl group.

[13] The composition according to any one of [7] to [12], further including (F) a benzotriazole-based compound in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyamide resin of (A). Photosensitive resin composition.

[14] A photosensitive resin composition solution comprising the photosensitive resin composition according to any one of [7] to [13] above and a solvent.

[15] The photosensitive resin composition according to any one of the above [7] to [13] or the photosensitive resin composition solution according to the above [14] is applied on a substrate, and the photosensitive resin composition is applied. Forming a coating film of
An exposure step of irradiating the coating film with actinic rays directly or through a patterning mask;
A development method of forming a relief pattern by dissolving and removing unexposed portions of the coating film using a developer, and a method of forming a relief pattern by heating and curing the relief pattern .

[16] A semiconductor device having a cured relief pattern formed by the method for forming a cured relief pattern according to [15].

The polyamide resin of the present invention and the photosensitive resin composition containing the same can provide a resin film exhibiting excellent chemical resistance even under low temperature heat curing conditions such as 200 ° C. or lower. The present invention also provides a method for forming a cured relief pattern excellent in chemical resistance using the photosensitive resin composition, and a semiconductor device having a cured relief pattern formed by the method.

Hereinafter, the present invention will be specifically described. 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.

<Polyamide resin>
In one embodiment, the present invention provides the following formula (1):

{Wherein X is a trivalent organic group having 6 to 15 carbon atoms, m is 0 or 2, and Y is a divalent organic group having 6 to 35 carbon atoms when m = 0, When m = 2, it is a tetravalent organic group having 6 to 35 carbon atoms, and R ₁ is a radically polymerizable unsaturated bond group having 5 to 20 carbon atoms, which may contain atoms other than carbon. It is an aliphatic group having at least one. Are included so that the number of repetitions is in the range of 2 to 150 and the number of repetitions is in the range of 80 to 100% of the total number of all the structural units constituting the polyamide resin. provide.

In this embodiment, the number of repeating structural units represented by the above formula (1) in one molecule of the polyamide resin is 2 to 150, and if it is 2 or more, the requirements as a polymer expected by the present invention are satisfied. If it is 150 or less, it is preferable from the viewpoints of solubility in a diluting solvent when preparing a photosensitive resin composition, rapidity during development processing, and the like. The number of repeating units of the structural unit represented by the above formula (1) is more preferably 2 to 100. In the present specification, the number of repeating structural units means the number of the structural units present in one molecule, and the structural units may be repeated continuously or through other structural units. Also good.

In this embodiment, the ratio of the number of repeating structural units represented by the above formula (1) in the total number of all structural units constituting the polyamide resin is in the range of 80 to 100%. When the ratio is 80% or more, the photosensitive properties of the coating film composed of the photosensitive resin composition of the present invention can be improved to the extent expected by the present invention, and further, the mechanical properties after heat curing of the coating film and The heat resistance and chemical resistance can also be improved to the extent expected by the present invention. The ratio is preferably 85% or more. The structural unit of the polyamide resin may be only the structural unit represented by the above formula (1) from the viewpoint of photosensitive characteristics, heat resistance, and chemical resistance (that is, the ratio is 100%), but in the process of forming a semiconductor element. The polyamide resin has a structural unit other than the structural unit represented by the above (1) for the purpose of, for example, further improving the adhesion with various structural materials in contact with it or imparting various properties as desired. In this case, the ratio is 20% or less, preferably 15% or less. When the repeating number of the structural unit represented by the formula (1) is 2 and 3, the repeating number is 100% of the total number of all the structural units constituting the polyamide resin.

In another aspect, the present invention provides the following formula (2):

{Wherein X is a trivalent organic group having 6 to 15 carbon atoms, m is 0 or 2, and Y is a divalent organic group having 6 to 35 carbon atoms when m = 0, When m = 2, it is a tetravalent organic group having 6 to 35 carbon atoms, W is a divalent organic group having 6 to 15 carbon atoms, k is an integer of 1 or more, and (n + k) Is an integer of 5 to 150, and R ₁ is an aliphatic group having 5 to 20 carbon atoms which may contain atoms other than carbon and has at least one radical-polymerizable unsaturated bond group. Are provided so that the number of repetitions n in the above formula (2) is 80% or more of the total number of all structural units constituting the polyamide resin. In the above formula (2), the arrangement of the structure with the repetition number n and the structure with the repetition number k may be random or block.

K in the formula (2) is an integer of 1 or more, and (n + k) is an integer of 5 to 150 at the same time. When k is 1 or more, the effect of copolymerizing various structures represented by the number k of repetitions can be obtained. At the same time, when (n + k) is 5 or more, the requirements as a polymer expected by the present invention are satisfied, and when it is 150 or less, solubility in a diluting solvent when forming a photosensitive resin composition, or during development processing It is preferable in terms of rapidity. (N + k) is preferably 5 to 100.

In this embodiment, among the total number of all the structural units constituting the polyamide resin, the ratio of the number of structural units having the repeating number n in the above formula (2) (that is, n) is 80% or more. If the ratio is 80% or more, the photosensitive properties of the coating film made of the photosensitive resin composition of the present invention can be improved to the extent expected by the present invention, and the machine after the coating film is heat-cured. The physical properties, heat resistance, and chemical resistance can also be improved to the extent expected by the present invention. The ratio is preferably 85% or more.

In this aspect, the ratio of the number of structural units having the number k of repetitions in the above formula (2) (that is, k) in the total number of all structural units constituting the polyamide resin is 20% or less. If the ratio is 20% or less, the excellent photosensitivity, mechanical properties, heat resistance, and chemical resistance of the present invention are ensured, and at the same time, the adhesion to various constituent materials that are in contact with each other in the process of forming a semiconductor element is improved. In addition to further improvements, various characteristics can be imparted as desired. The ratio is preferably 15% or less. The polyamide resin in this embodiment may have only the structure represented by the above formula (2) as a structural unit from the viewpoint of achieving the photosensitive properties and mechanical properties, heat resistance, and chemical resistance that are the object of the present invention, You may have structural units other than the structure represented by the said Formula (2).

When the terminal of the polyamide resin of the present invention is a structural unit represented by the above formula (1) or (2), the molecular chain terminal is a carboxyl group derived from a dicarboxylic acid containing a trivalent organic group represented by X Or an amino group derived from a diamine containing a divalent or tetravalent organic group represented by Y, but various chemical modifications of the carboxyl group (for example, ester, amide, etc.) and various amino groups It may be a chemically modified product (for example, amide, urethane, imide, etc.).

In another aspect, the present invention provides the following formula (3):

{Wherein X is a trivalent organic group having 6 to 15 carbon atoms, m is 0 or 2, and Y is a divalent organic group having 6 to 35 carbon atoms when m = 0, When m = 2, it is a tetravalent organic group having 6 to 35 carbon atoms, W is a divalent organic group having 6 to 15 carbon atoms, l is 0 or an integer of 1 or more, and ( n + 1) is an integer of 2 to 150, and R ₁ is an aliphatic group having 5 to 20 carbon atoms which may contain atoms other than carbon and which has at least one radical-polymerizable unsaturated bond group. . } Is provided as a structural unit, and a polyamide resin having a repeating number n in the above formula (3) in the range of 80 to 100% of all structural units constituting the polyamide resin is provided. In the above formula (3), the arrangement of the structure with the repetition number n and the structure with the repetition number l may be random or block.

In the formula (3), (n + 1) is 2 to 150, and if it is 2 or more, the requirements as a polymer expected by the present invention are satisfied, and if it is 150 or less, a photosensitive resin composition is obtained. Is preferable in terms of solubility in a diluting solvent and rapidity during development processing. The repeating number of the structural unit represented by the above formula (3) is preferably 2 to 100.

In this embodiment, the ratio of the number of repeating units represented by repeating unit n out of the total number of all constituting units constituting the polyamide resin is in the range of 80 to 100%. When the ratio is 80% or more, the photosensitive properties of the coating film composed of the photosensitive resin composition of the present invention can be improved to the extent expected by the present invention, and further, the mechanical properties after heat curing of the coating film and The heat resistance and chemical resistance can also be improved to the extent expected by the present invention. The ratio is preferably 85% or more. The constitutional unit of the polyamide resin may be only the constitutional unit represented by the repeating unit n (the ratio of n is 100%) from the viewpoint of photosensitive characteristics, heat resistance, and chemical resistance, but is in contact in the process of forming a semiconductor element. It is also preferable to have a structural unit represented by a repeating unit 1 for the purpose of further improving the adhesion with various structural materials or imparting various properties as desired, in which case the above ratio is It is 20% or less, and preferably 15% or less. When the constitutional unit represented by the repeating unit 1 is 20% or less of the total number of all constitutional units, various properties can be obtained as desired while ensuring the photosensitive properties, mechanical properties, heat resistance, and chemical resistance achieved in the present invention. It is possible to impart the characteristics of When (n + 1) is 2 to 4, the structural unit represented by the repeating unit n is 100% of the total number of all structural units constituting the polyamide resin.

The molecular chain terminal of the polyamide resin in this embodiment is a carboxyl group derived from a dicarboxylic acid containing a trivalent organic group represented by X, a carboxyl group derived from a dicarboxylic acid containing a divalent organic group represented by W, or Y Is a diamine-derived amino group containing a divalent or tetravalent organic group represented by the formula, but various chemical modifications of the carboxyl group (for example, ester, amide, etc.) and various chemical modifications of the amino group (For example, an amide body, a urethane body, an imide body, etc.) may be sufficient.

In the above formulas (1) to (3), R ₁ is an aliphatic group having 5 to 20 carbon atoms which may contain atoms other than carbon and has at least one radical-polymerizable unsaturated bond group. is there. R ₁ is represented by the following formula (4) from the viewpoint of photosensitive characteristics and chemical resistance:

{In the formula, R ₂ 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 characteristics, R ₁ is preferably a group having at least one (meth) acryloyloxymethyl group.

In the above formulas (1) to (3), the trivalent organic group represented by X 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. It is a group. In formulas (1) to (3), the divalent or tetravalent organic group represented by Y is an 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. In the formulas (2) and (3), the divalent organic group represented by W is a divalent organic group having 6 to 15 carbon atoms from the viewpoint of photosensitive properties, heat resistance, heat resistance, chemical resistance, and the like. It is a group. W is a structure obtained by removing two carboxyl group-derived moieties from the structure of dicarboxylic acid or its derivative.

In the present invention, from the viewpoints of photosensitive properties, mechanical properties, heat resistance, chemical resistance, etc., the above W, X and Y are each independently an aromatic group, alicyclic group, aliphatic group, siloxane group. And a group selected from the group consisting of groups of these complex structures.

In the above formulas (1) to (3), X is 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 formulas (1) to (3), Y represents a cyclic organic group having 1 to 4 aromatic or aliphatic rings which may be substituted, or an aliphatic group or siloxane group having no cyclic structure. It is more preferable. Specifically, preferred examples of the cyclic organic group include the following aromatic groups or alicyclic groups:

（式中、Ａは、それぞれ独立に、水酸基、メチル基、エチル基、プロピル基およびブチル基からなる群から選ばれる１つの基であり、プロピル基およびブチル基にあっては、各種異性体も含む。）

(In the formula, each A is independently one group selected from the group consisting of a hydroxyl group, a methyl group, an ethyl group, a propyl group, and a butyl group. 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 formula, 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 the substituent B, and B represents a substituent on the ring, particularly 1 to 4 hydrocarbon groups are represented.

In addition, preferable examples of the aliphatic group or siloxane group having no cyclic structure include 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.

W in formulas (2) and (3) is preferably an aromatic group, an aliphatic group or an alicyclic group, respectively. Preferred aromatic groups include the following groups:

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

Synthesis of phthalic acid compound encapsulated body First, a compound having a trivalent aromatic group X (a group corresponding to X in the above formulas), for example, phthalic acid substituted with an amino group, substituted with an amino group 1 mol or more of a compound selected from the group consisting of terephthalic acid substituted with an amino group and terephthalic acid substituted with an amino group (hereinafter referred to as “phthalic acid compound”), and one or more types that react with an amino group A compound obtained by reacting with 1 mol of a compound and modifying and sealing the amino group of the phthalic acid compound with one or more groups containing a radical polymerizable unsaturated bond described later (hereinafter referred to as “phthalic acid compound sealing”). Body)).

A structure in which a phthalic acid compound is sealed with a group containing the above 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 encapsulated phthalic acid compound includes an aliphatic acid chloride having 5 to 20 carbon atoms, an aliphatic isocyanate, or an aliphatic epoxy compound 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 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.

The reaction solvent is preferably one that completely dissolves the product phthalic acid compound encapsulant, such as 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 can 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, in order to prevent contamination in the subsequent steps, the product is once again re-precipitated with water, washed with water and dried, or passed through a column filled with ion exchange resin to reduce or reduce ionic components. It is preferable to carry out.

Synthesis of polyamide resin Secondly, 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 formulas) are mixed with pyridine, triethylamine or the like. The polyamide resin of the present invention can be obtained by mixing in an appropriate solvent in the presence of a basic catalyst and subjecting it to amide polycondensation.

If desired, a part of the sealed phthalic acid compound can be used in combination with a dicarboxylic acid having a divalent organic group W (a group corresponding to W in the above formulas). About the combined use ratio, it is preferable that the ratio of the number of structures derived from the sealed phthalic acid compound in the total number of all structural units of the polyamide resin is 80% or more and 100% or less. When the combined ratio is used, it is possible to improve the photosensitive characteristics at the time of ultraviolet exposure and the film characteristics after heat curing, particularly chemical resistance, to the level expected by the present invention.

As the amide polycondensation method, a dicarboxylic acid component (a phthalic acid compound encapsulated body and a dicarboxylic acid having a divalent organic group W; the same shall apply hereinafter) was converted into a symmetric polyacid anhydride using a dehydrating condensing agent. A method of mixing with a diamine compound later, a method of mixing a dicarboxylic acid component with an acid chloride by a known method and then mixing with a diamine compound, and reacting a dicarboxylic acid component with an active esterifying agent in the presence of a dehydrating condensing agent A method of mixing the product with a diamine compound after esterification is exemplified.

Preferred dehydration condensing agents include, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1′-carbonyldioxy-di-1,2,3-benzotriazole, N, Examples thereof include N′-disuccinimidyl carbonate.

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- And 2-cyanoacetamide.

Examples of the dicarboxylic acid having a divalent organic group W include phthalic acid, isophthalic acid, terephthalic acid, 4,4′-diphenyl ether dicarboxylic acid, 3,4′-diphenyl ether dicarboxylic acid, 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) Fido, bis (4-carboxyphenyl) tetraphenyldisiloxane, bis (4-carboxyphenyl) tetramethyldisiloxane, bis (4-carboxyphenyl) sulfone, bis (4-carboxyphenyl) methane, 5-tert-butylisophthal 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 -Dicarboxyphenyl) -N'-ethoxycarbonylurea, N- (3,5-dicarboxyphenyl) norborneneimide, 2,2-bis- (p-carboxyphenyl) propane, 4,4 '-(p-pheny Rangeoxy) dibenzoic acid, 2,6-naphthalenedicarboxylic acid In addition to the above aromatic dicarboxylic acids, 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 Aliphatic dicarboxylic acids such as 1,3-dicarboxylic acid and alicyclic dicarboxylic acids.

The diamine compound having an organic group Y is at least one diamine selected from the group consisting of an aromatic diamine compound, an aromatic bisaminophenol compound, an alicyclic diamine compound, a linear aliphatic diamine compound, and a siloxane diamine compound. A compound is preferable, and a plurality of 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'- Aminodiphenylmethane, 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 4-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 their benzene rings Examples thereof include diamine compounds in which a part of hydrogen 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 a hydrogen atom on the benzene ring is 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.

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'- Aminodiphenyl ether, 4,4′-dihydroxy-3,3′-diaminodiphenylether, 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 alicyclic diamine compounds 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 4,4'-methylenebis (cyclohexylamine), 4,4'-methylenebis (2-methylcyclohexylamine), 1,4-bis (3-aminopropyl) piperazine, 3,9-bis (3-aminopropyl)- Examples include 2,4,8,10-tetraoxaspiro- [5,5] -undecane.

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. 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.

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, in some cases, ketones, esters, lactones, ethers, hydrocarbons, and halogenated hydrocarbons may be used as a reaction solvent. 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 dehydrating 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 7,000 to 70,000, and 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 GPC eluents. Moreover, a weight average molecular weight value is calculated | required from the calibration curve created using standard monodisperse polystyrene. The standard monodisperse polystyrene is recommended to be selected from Showa Denko's organic solvent standard sample STANDARD SM-105.

<Photosensitive resin composition>
The present invention relates to a photosensitive resin composition comprising (A) 100 parts by mass of the above-described polyamide resin of the present invention (hereinafter also referred to as (A) polyamide resin) and (B) 0.5-20 parts by mass of a photopolymerization initiator. Things are also provided. Specific embodiments of the (A) polyamide resin that can be used in the photosensitive resin composition of the present invention are as described above. In the photosensitive resin composition of the present invention, from the viewpoint of imparting photosensitive characteristics, the (A) polyamide resin and (B) photopolymerization initiator are used in combination.

(B) Photopolymerization initiator (B) As the photopolymerization initiator, any conventionally known compound can be used as a photopolymerization initiator for polyamide. As a preferable example, for example,
[1] Benzophenone, benzophenone derivatives such as methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone, etc. [2] 2,2′-diethoxyacetophenone, 2-hydroxy-2- Methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- Acetophenone derivatives such as 1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] -phenyl} -2-methylpropan-1-one, methyl phenylglyoxylate [3] Thioxanthone, 2-methylthioxanthone, 2-isopropylthioxyl Thioxanthone derivatives such as benzone, diethylthioxanthone [4] benzyl derivatives such as benzyl, benzyldimethyl ketal and benzyl-β-methoxyethyl acetal [5] benzoin, benzoin methyl ether, 2-hydroxy-2-methyl-1-phenylpropane- Benzoin derivatives such as 1-one

[6] 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1, 2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanetrione-2- (O-ethoxycarbonyl) ) Oxime, 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone , 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), etc. Xime compounds [7] 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1 Α-hydroxy ketone compounds such as 2-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropane [8] 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butane-1 Α-aminoalkylphenone compounds such as —one [9] bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzo) Yl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and other phosphine oxide compounds [10] bis (η ⁵ -2,4-cyclo And titanocene compounds such as pentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium. Moreover, these photoinitiators can be used individually or in mixture of 2 or more types as desired.

Among the photopolymerization initiators described above, the oxime [6] is more preferable particularly from the viewpoint of photosensitivity. The blending amount of the (B) photopolymerization initiator with respect to 100 parts by mass of the (A) polyamide resin is preferably 0.5 to 20 parts by mass, and more preferably 1 to 10 parts by mass. When the blending amount is 0.5 parts by mass or more, radicals sufficient to allow photoradical polymerization to proceed sufficiently are supplied during exposure, ensuring sufficiently good photosensitivity for practical use, and a relief pattern suitable for practical use. Can be obtained. Moreover, when the said compounding quantity is 20 mass parts or less, when exposing the board | substrate with which the photosensitive resin composition was apply | coated, since an exposure light beam can be made to reach | attain to the board | substrate surface vicinity, it is uniform in the film thickness direction. Radical photopolymerization can proceed, and a relief pattern suitable for practical use can be obtained.

(C) Monomer having photopolymerizable unsaturated bond The photosensitive resin composition of the present invention comprises (C) a monomer having a photopolymerizable unsaturated bond in order to improve the photosensitive properties such as sensitivity and resolution. Further, it can be included. (C) The monomer having a photopolymerizable unsaturated bond is preferably a (meth) acrylic compound that can be radically polymerized by the above-mentioned (B) photopolymerization initiator. For example, polyethylene glycol diacrylate (for each ethylene glycol unit) 2 to 20), polyethylene glycol dimethacrylate (number 2 to 20 of each ethylene glycol unit), poly (1,2-propylene glycol) diacrylate, poly (1,2-propylene glycol) dimethacrylate, pentaerythritol diacrylate , Pentaerythritol dimethacrylate, glycerol diacrylate, glycerol dimethacrylate, dipentaerythritol hexaacrylate, methylenebisacrylamide, N-methylolacrylamide, ethylene glycol jig Ricidyl ether-methacrylic acid adduct, glycerol diglycidyl ether-acrylic acid adduct, bisphenol A diglycidyl ether-acrylic acid adduct, bisphenol A diglycidyl ether-methacrylic acid adduct, N, N′-bis (2- And methacryloyloxyethyl) urea. These may be used alone or in admixture of two or more as required.

(A) The blending amount of the monomer (C) having a photopolymerizable unsaturated bond with respect to 100 parts by mass of the polyamide resin is preferably 1 to 40 parts by mass, and more preferably 1 to 20 parts by mass. When the blending amount is 1 part by mass or more, the photocrosslinking (photo radical polymerization) at the exposed part proceeds sufficiently during exposure, and a sufficiently good photosensitivity is ensured for practical use, and a relief pattern suitable for practical use. Can be obtained. In addition, when the blending amount is 40 parts by mass or less, it is possible to suppress unnecessary photocuring in the unexposed area due to light spots from the exposed area, that is, a post-development residue, and a relief pattern suitable for practical use. Can be obtained. Furthermore, the residual monomer component which becomes a degassing component from the cured film can be suppressed even at low temperature curing, which is preferable.

(D) Thermally crosslinkable compound The photosensitive resin composition of the present invention can further contain (D) a thermally crosslinkable compound in order to improve film properties (particularly heat resistance) after heat curing. (D) Thermally crosslinkable compound is (A) a compound that thermally crosslinks a polyamide resin, or a compound that itself forms a thermally crosslinked network. (D) 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) The blending amount of the (D) thermally crosslinkable compound with respect to 100 parts by mass of the polyamide resin is preferably 1 to 20 parts by mass, and more preferably 3 to 15 parts by mass. When the said compounding quantity is 1 mass part or more, the film | membrane characteristic after heat-hardening of the photosensitive resin composition of this invention can be improved further. Moreover, when the said compounding quantity is 20 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.

(E) Silane coupling agent The photosensitive resin composition of the present invention preferably contains (E) a silane coupling agent in order to improve photosensitive properties such as adhesion during development. (E) As a silane coupling agent, an organosilicon compound having a (dialkoxy) monoalkylsilyl group or a (trialkoxy) silyl group is preferable, for example, a compound represented by the following formula:

{In the formula, g is an integer of 1 or 2; when g is 1, Z is a divalent aromatic group; when g is 2, Z is a tetravalent aromatic group; A divalent organic group containing a carbon atom directly bonded to a silicon atom, d is an integer of 0 or 1, R ₅ is a hydrogen atom or a monovalent hydrocarbon group, and R ₆ and R ₇ are respectively Independently, it is an alkyl group having 1 to 4 carbon atoms, and e is an integer of 0 or 1. }.

The silane coupling agent is 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. Can do.

As dicarboxylic acid anhydride or tetracarboxylic dianhydride, and derivatives thereof, various structures can be used. For example, 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 tetra Rubonic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl Tetracarboxylic dianhydride etc. are mentioned.

Of these, phthalic anhydride and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride are particularly preferred in view of the effect of excellent adhesion to the base substrate and the price.

As the (dialkoxy) monoalkylsilyl compound and (trialkoxy) silyl compound having an amino group, various structures can be used, and examples thereof include the following (hereinafter, the notation of alkoxy is methoxy group or ethoxy). Refers to the group):
2-aminoethyltrialkoxysilane, 3-aminopropyltrialkoxysilane, 3-aminopropyl dialkoxymethylsilane, 2-aminoethylaminomethyltrialkoxysilane, 2-aminoethylaminomethyldialkoxymethylsilane, 3- (2 -Aminoethylaminopropyl) trialkoxysilane, 3- (2-aminoethylaminopropyl) dialkoxymethylsilane, 3-allylaminopropyltrialkoxysilane, 2- (2-aminoethylthioethyl) trialkoxysilane, 2- (2-aminoethylthioethyl) dialkoxymethylsilane, 3-piperazinopropyltrialkoxysilane, 3-piperazinopropyl dialkoxymethylsilane, cyclohexylaminopropyltrialkoxysilane and the like.

In view of the effect of adhesion to the base substrate and the price, 3-aminopropyltriethoxysilane is particularly suitable.

In addition, those mentioned above as (dialkoxy) monoalkylsilyl compounds and (trialkoxy) silyl compounds having an amino group may be used as they are as silane coupling agents.

Further, N-trialkoxysilyl-1,2,4-triazole, N-trialkoxysilylimidazole, N-trialkoxysilylpyrrole, N-trialkoxysilylpyridine, N-trialkoxysilylpyrrolidine, piperidinomethyltrialkoxy Silane, 2-piperidinoethyltrialkoxysilane, 3-morpholinopropyltrialkoxysilane, 3-piperazinopropyltrialkoxysilane, 3-piperidinopropyltrialkoxysilane, 3- (4-methylpiperazinopropyl) ) Trialkoxysilane, 3- (4-methylpiperidinopropyl) trialkoxysilane, 4- (2-trialkoxysilylethyl) pyridine, N- (3-trialkoxysilylpropyl) -4,5-dihydroimidazole, 2- (2-Tria Job Shi silyl ethyl) pyridine, N-(3- trialkoxysilylpropyl) organosilicon compound heterocyclic containing such pyrrole and the like.

Further, vinyltrialkoxyxysilane, 1-propenyltrialkoxysilane, 2-propenyltrialkoxysilane, 3-methacryloyloxypropyltrialkoxysilane, 3-acryloyloxypropyltrialkoxysilane, 3-methacryloxypropylmethyl dialkoxylane, Containing carbon-carbon unsaturated bonds such as 3-acryloxypropylmethyl dialkoxylane, p-styryltrialkoxysilane, p- (1-propenylphenyl) trialkoxysilane, p- (2-propenylphenyl) trialkoxysilane An organosilicon compound is mentioned.

Further, 2- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropylmethyldialkoxysilane, p-styryltrialkoxysilane, N-2 (aminoethyl) -3-aminopropyltrialkoxysilane, N- (2-aminoethyl) -3-aminopropylmethyl dialkoxysilane, 3-trialkoxysilyl-N- (1.3-dimethyl-butylidene) propylamine, N-phenyl -3-aminopropyltrialkoxysilane, 3-ureidopropyltrialkoxysilane, 3-ureidopropylmethyldialkoxysilane, 3-mercaptopropyltrialkoxysilane, 3-mercaptopropylmethyldialkoxysilane, bis (trialkoxy Rylpropyl) tetrasulfide, 3-isocyanatopropyltrialkoxysilane, 6-trialkoxysilyl-2-norbornene, dialkoxydodecylmethylsilane, 3- (trialkoxysilyl) propylsuccinic anhydride, N- (3-di Alkoxymethylsilylpropyl) succinimide, N- [3- (trialkoxysilyl) propyl] phthalamic acid, N- [3- (trialkoxysilyl) propyl] phthalimide, N- [3- (dialkoxysilyl) propyl] phthalimide, etc. Is mentioned.

(E) The silane coupling agent may be used alone or as a mixture of two or more. The blending amount of the (E) silane coupling agent with respect to 100 parts by mass of the (A) polyamide resin is preferably 0.1 to 25 parts by mass, and more preferably 0.3 to 20 parts by mass. 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 silane coupling agents in the photosensitive resin composition reduces significantly.

(F) Benzotriazole-based compound The photosensitive resin composition of the present invention improves adhesion of the photosensitive resin on a substrate (particularly a copper substrate) or suppresses discoloration of the copper substrate. F) It is preferable to contain a benzotriazole-based compound. Examples of (F) benzotriazole compounds include benzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole, 4 (or 5) -carboxybenzotriazole, 4 (or 5)- Methylbenzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] -4 (or 5) -methylbenzotriazole, 1- [N, N-bis (hydroxyethyl) aminomethyl] -4 (or 5) -Methylbenzotriazole, 1-hydroxymethylbenzotriazole, 1-[(2-ethylhexylamino) methyl] -benzotriazole, 1- (1 ′, 2′-dicarboxyethyl) benzotriazole, N-benzotriazoyl Methylurea, 2,6-bis [(1H-benzotriazol-1-yl) me L] 4-methylphenol, 1- (2,3-dicarboxypropyl) benzotriazole, 2-tert-butyl-4-methyl-6-[(1H-benzotriazol-1-yl) methyl] phenol, 2, 4-di-tert-butyl-6-[(1H-benzotriazol-1-yl) methyl] phenol, 4 (or 5) -nitrobenzotriazole and the like.

Of these, 4 (or 5) -carboxybenzotriazole and 4 (or 5) -methylbenzotriazole are particularly preferable.

(F) The benzotriazole-based compound may be a single compound or a mixture of two or more. The blending amount of the (F) benzotriazole compound with respect to 100 parts by mass of the (A) polyamide resin is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass. When the said compounding quantity is 0.1 mass part or more, the adhesiveness of the photosensitive resin on a board | substrate (especially copper substrate) improves, and the effect which suppresses discoloration of a copper substrate expresses favorably. Moreover, when the said compounding quantity is 10 mass parts or less, the fall of the adhesiveness of the photosensitive resin on a board | substrate (especially copper substrate) can be suppressed.

Other components: Sensitizer If desired, the photosensitive resin composition may contain a sensitizer for improving photosensitivity. Examples of such sensitizers include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzylidene) cyclopentanone, and 2,6-bis (4′-diethylamino). Benzylidene) cyclohexanone, 2,6-bis (4′-dimethylaminobenzylidene) -4-methylcyclohexanone, 2,6-bis (4′-diethylaminobenzylidene) -4-methylcyclohexanone, 4,4′-bis (dimethylamino) ) Chalcone, 4,4′-bis (diethylamino) chalcone, 2- (4′-dimethylaminocinnamylidene) indanone, 2- (4′-dimethylaminobenzylidene) indanone, 2- (p-4′-dimethylamino) Biphenyl) benzothiazole, 1,3-bis (4-dimethylaminobenzylide) ) Acetone, 1,3-bis (4-diethylaminobenzylidene) acetone, 3,3′-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethyl Aminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, N, N-bis (2-hydroxyethyl) aniline, 4-morpholinobenzophenone, isoamyl 4-dimethylaminobenzoate, isoamid 4-diethylaminobenzoate 1,2,3-benzotriazole, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, 1-cyclohexyl-5-mercapto-1,2,3,4 -Tetrazole, 1- (tert-butyl) -5-mercapto-1,2,3,4-tetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylamino) Styryl) benzthiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-p) thiazole, 2- (p-dimethylaminobenzoyl) styrene and the like.

The sensitizer used may be a single or a mixture of two or more. The blending amount of the sensitizer is preferably 0 to 15 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the (A) polyamide resin.

Other components: Polymerization inhibitor The photosensitive resin composition of the present invention contains a polymerization inhibitor, if desired, for the purpose of improving the viscosity of the photosensitive resin composition solution during storage and the stability of photosensitivity. It can also be made. Examples of such 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-phenylhydroxyamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt ,Screw 4-hydroxy-3,5-di-tert- butyl) phenyl methane, or the like can be used.

The blending amount of the polymerization inhibitor is preferably 0 to 5 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the (A) polyamide resin. When the said compounding quantity is 5 mass parts or less, the photosensitivity suitable for practical use can be ensured favorably, without inhibiting the photocrosslinking reaction anticipated.

In the photosensitive resin composition of the present invention, various additives such as a scattered light absorber and a coating film smoothness-imparting agent are added to the photosensitive resin composition according to need, as long as they do not inhibit the effects of the present invention. Can be appropriately blended.

<Photosensitive resin composition solution>
The present invention also provides a photosensitive resin composition solution comprising the above-described photosensitive resin composition of the present invention and a solvent. It is preferable to use a photosensitive resin composition solution whose viscosity is adjusted by adding a solvent to the photosensitive resin composition. Suitable solvents include N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, cyclopentanone , Γ-butyrolactone, α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, etc., and these may be used alone or in combination of two or more. Can be used. Among these, N-methyl-2-pyrrolidone and γ-butyrolactone are particularly preferable.

These solvents can be appropriately added to the photosensitive resin composition of the present invention depending on the coating film thickness and viscosity of the photosensitive resin composition solution. It is preferable to use in the range of 1,000 parts by mass.

In order to improve the storage stability and the like of the photosensitive resin composition, as a solvent, in addition to the above, alcohols shown below can be used in combination. The alcohol is not particularly limited as long as it has an alcoholic hydroxyl group in the molecule, but specific examples include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol. , T-butyl alcohol, benzyl alcohol, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monoethyl ether, propylene glycol diethyl ether, propylene glycol mono (n-propyl) ether, propylene glycol di (n -Propyl) ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono (n-propyl) ether Ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, mono alcohols such as diethylene glycol monophenyl ether, ethylene glycol, and di alcohols such as propylene glycol. Among these, benzyl alcohol and ethylene glycol monophenyl ether are particularly preferable.

When these alcohols are used in combination, the content ratio in the entire solvent is preferably 50% by mass or less. When the said ratio exceeds 50 mass%, there exists a tendency for the solubility with respect to this solvent of (A) polyamide resin to fall.

<Method for forming cured relief pattern>
The present invention includes a step of applying the above-described photosensitive resin composition of the present invention or the photosensitive resin composition solution of the present invention on a substrate to form a coating film of the photosensitive resin composition, the coating film An exposure step of irradiating actinic rays directly or through a patterning mask, a development step of forming a relief pattern by dissolving and removing unexposed portions of the coating film using a developer, and curing by curing the relief pattern by heating There is also provided a method for forming a cured relief pattern comprising a step of forming a relief pattern. The example of the formation method of the hardening relief pattern of this invention is demonstrated below.

First, the photosensitive resin composition or the photosensitive resin composition solution of the present invention is applied on a base material such as a silicon wafer, an aluminum substrate, or a copper substrate. As the coating apparatus or coating method, a spin coater, a die coater, a spray coater, dipping, printing, a blade coater, roll coating, or the like can be used. The coating film is dried by pre-baking at 80 to 120 ° C. to form a coating film of the photosensitive resin composition to a film thickness of about 5 to 50 microns.

Next, the coating film formed above is irradiated with actinic rays directly or through a desired patterning mask (photomask) using an exposure projection apparatus such as a contact aligner, mirror projection, or stepper. Exposure. As the actinic rays, X-rays, electron beams, ultraviolet rays, visible rays and the like can be used. In the present invention, actinic rays having a wavelength of 200 to 500 nm are preferably used.

After the exposure, post-exposure baking or pre-development baking with any combination of temperature and time (preferably temperature 40 ° C. to 120 ° C., time 10 seconds to 240 seconds) is performed as necessary for the purpose of improving photosensitivity. You may give it.

Next, development is performed to form a relief pattern by dissolving and removing unexposed portions of the coating film using a developer. The developing method can be selected from methods such as an immersion method, a paddle method, and a rotary spray method. As the developer, a good solvent for polyamide can be used alone, or a good solvent and a poor solvent for polyamide can be appropriately mixed and used. Good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, gamma butyrolactone, α-acetyl-gammabutyrolactone, cyclopenta Non, cyclohexanone and the like, and toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, water and the like can be used as the poor solvent, respectively.

When a good solvent and a poor solvent are mixed and used, the mixing ratio is adjusted according to the solubility of the polyamide resin used, the developing method used, and the like.

For example, when aromatic bisaminophenol is used as all or part of the 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 as a developer. 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.

After completion of development, a relief pattern can be obtained by washing with a rinsing solution as necessary and removing the developer. As the rinsing liquid, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. can be used alone or in appropriate combination of two or more, and two or more can be used. It can also be used in combination in stages.

The relief pattern of the polyamide thus obtained is a cured relief pattern made of polyamide having excellent heat resistance and chemical resistance by appropriately heating, for example, to 150 to 350 ° C. to advance heat curing and crosslinking reaction. Is converted to Such a heat curing process can be performed using a hot plate, an inert oven, a temperature rising oven capable of setting a temperature program, or the like. Air may be used as the atmosphere for heat curing, and an inert gas such as nitrogen or argon may be used.

<Semiconductor device>
The present invention also provides a semiconductor device having a cured relief pattern formed by the above-described method for forming a cured relief pattern of the present invention. The cured relief pattern produced as described above is used as a surface protection film, an interlayer insulation film, an α-ray shielding film, a partition, a dam, etc. of a semiconductor device built on a substrate such as a silicon wafer. A semiconductor device can be manufactured by applying a known method for manufacturing a semiconductor device in the process. It is also possible to obtain a semiconductor device having a coating film made of a resin obtained by curing the above-described photosensitive resin composition of the present invention.

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 sealed phthalate compound AIPA-MO)
In a separable flask having a volume of 5 liters, 5-aminoisophthalic acid {hereinafter abbreviated as AIPA. } 543.5 g (3.0 mol), N-methyl-2-pyrrolidone {hereinafter referred to as NMP. } 1700 g was added, mixed and stirred, and heated to 50 ° C. with a water bath. To this, 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate is referred to as gamma-butyrolactone {hereinafter referred to as GBL. } The one diluted with 500 g was added dropwise with a dropping funnel and stirred at 50 ° C. for about 2 hours.

The completion of the reaction (disappearance of 5-aminoisophthalic acid) is described as 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 and allowed to stand. After the reaction product was crystallized and precipitated, it was filtered, washed with water, and vacuumed at 40 ° C. for 48 hours. By drying, AIPA-MO in which the amino group of 5-aminoisophthalic acid and the isocyanate group of 2-methacryloyloxyethyl isocyanate were acted was obtained. The obtained AIPA-MO had a low molecular weight GPC purity of almost 100%.

[Synthesis Example 2]
(Synthesis of Phthalic Acid Compound Encapsulated AIPA-BA)
AIPA 543.5 g (3.0 mol) and NMP 1700 g were charged into a 5 liter separable flask, mixed and stirred, and heated to 50 ° C. in a water bath. A solution prepared by diluting 789.46 g (3.3 mol) of 1,1-bis (acryloyloxymethyl) ethyl isocyanate with 500 g of GBL was added dropwise to this with a dropping funnel, and the mixture was stirred at 50 ° C. for about 2 hours.

After confirming the completion of the reaction (disappearance of AIPA) by low molecular weight GPC, the reaction solution was poured into 15 liters of ion-exchanged water, stirred and allowed to stand, and filtered after waiting for crystallization precipitation of the reaction product. After appropriately washing with water and vacuum drying at 40 ° C. for 48 hours, AIPA-BA in which the amino group of AIPA and the isocyanate group of 1,1-bis (acryloyloxymethyl) ethyl isocyanate acted was obtained. The obtained AIPA-BA had a low molecular weight GPC purity of almost 100%.

[Synthesis Example 3]
(Synthesis of Phthalic Acid Compound Encapsulated AIPA-ME)
AIPA 543.5 g (3.0 mol) and NMP 1700 g were charged into a 5 liter separable flask, mixed and stirred, and heated to 50 ° C. in a water bath. A solution obtained by diluting 657.38 g (3.3 mol) of 2- (2-methacryloyloxyethoxy) ethyl isocyanate with 500 g of GBL was added dropwise to this with a dropping funnel, and the mixture was stirred at 50 ° C. for about 2 hours.

After confirming the completion of the reaction (disappearance of AIPA) by low molecular weight GPC, the reaction solution was poured into 15 liters of ion-exchanged water, stirred and allowed to stand, and filtered after waiting for crystallization precipitation of the reaction product. After appropriately washing with water and vacuum drying at 40 ° C. for 48 hours, AIPA-ME in which the amino group of AIPA and the isocyanate group of 2- (2-methacryloyloxyethoxy) ethyl isocyanate were reacted was obtained. The obtained AIPA-ME had a low molecular weight GPC purity of almost 100%.

[Synthesis Example 4]
(Synthesis of phthalic acid compound sealing body AIPA-NBI)
AIPA 543.5 g (3.0 mol) and NMP 1700 g were charged into a 5 liter separable flask, mixed and stirred, and heated to 50 ° C. in a water bath. A solution obtained by diluting 541.73 g (3.3 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride with 500 g of GBL was added dropwise thereto with a dropping funnel, and the mixture was stirred at 50 ° C. for about 10 hours.

The completion of the reaction (disappearance of AIPA) was confirmed by low molecular weight GPC, and the completion of norbornene imidization (disappearance of carboxyl group) was confirmed by FT-IR spectrum analysis, and then the reaction solution was added to 15 liters of ion-exchanged water. The mixture was allowed to stand, stirred, and allowed to stand. After the crystallization and precipitation of the reaction product, the solution was filtered off, washed with water as appropriate, and dried in vacuo at 40 ° C. for 48 hours, whereby the amino group of AIPA and 5-norbornene-2,3 -AIPA-NBI having a norbornene imide structure was obtained by the action of an acid anhydride group of dicarboxylic acid anhydride. The obtained AIPA-NBI had a low molecular weight GPC purity of almost 100%.

[Synthesis Example 5]
(Synthesis of phthalic acid compound sealing body AIPA-MA)
In a separable flask having a volume of 5 liters, 543.5 g (3.0 mol) of AIPA and 1700 g of NMP were added and mixed and stirred. A solution obtained by diluting 344.97 g (3.3 mol) of methacrylic acid chloride with 500 g of GBL was added dropwise thereto using a dropping funnel, and the mixture was stirred at room temperature for about 2 hours.

After confirming the completion of the reaction (disappearance of AIPA) by low molecular weight GPC, the reaction solution was poured into 15 liters of ion-exchanged water, stirred and allowed to stand, and filtered after waiting for crystallization precipitation of the reaction product. After appropriately washing with water and vacuum drying at 40 ° C. for 48 hours, AIPA-MA in which the amino group of AIPA and the acid chloride group of methacrylic acid chloride acted was obtained. The obtained AIPA-MA had a low molecular weight GPC purity of almost 100%.

[Synthesis Example 6]
(Synthesis of silane coupling agent S-1)
A 1 L round bottom flask was charged with 32.2 g (0.1 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and 206 g of NMP, 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 the dropwise addition, this was returned to room temperature and stirred for 4 hours, whereby the acid anhydride group of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and the amino group of 3-aminopropyltriethoxysilane Reacted to give a 20% by mass NMP solution of the half-acid / half-amidated silane coupling agent S-1.

[Synthesis Example 7]
(Synthesis of silane coupling agent S-2)
A 1 L round bottom flask was charged with 29.6 g (0.2 mol) of phthalic anhydride and 195 g of N-methyl-2-pyrrolidone, and stirring was started. While this solution was cooled to 0 ° C. and maintained, a solution prepared by diluting 3-aminopropyltriethoxysilane with 44.2 g (0.2 mol) of NMP (100 g) was added dropwise. After completion of the dropwise addition, this is returned to room temperature and stirred for 4 hours, whereby the acid anhydride group of phthalic anhydride reacts with the amino group of 3-aminopropyltriethoxysilane to form a half acid / half amidated silane cup. A 20 mass% NMP solution of ring agent S-2 was obtained.

[Synthesis Example 8]
(Synthesis of polyamide PA-1)
Into a separable flask having a volume 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 an ice bath At 5 ° C. This is N, N-dicyclohexylcarbodiimide {hereinafter referred to as DCC. } A solution obtained by dissolving 125.0 g (0.606 mol) in 125 g of GBL was added dropwise over about 20 minutes under ice cooling, followed by 4,4′-bis (4-aminophenoxy) biphenyl {hereinafter referred to as BAPB) I write. } 103.16 g (0.28 mol) dissolved in 168 g of NMP was added dropwise over about 20 minutes, 3 hours while maintaining the temperature below 5 ° C. in an ice bath, and then the ice bath was removed and stirred at room temperature for 5 hours. did.

Then, dicyclohexylurea derived from a dehydrating condensing agent, which was precipitated in the polycondensation process {hereinafter referred to as DCU]. } Was filtered under pressure, and while stirring the filtrate (polymer solution), a mixed solution of 840 g of water and 560 g of isopropanol was dropped, and the precipitated polymer was separated and redissolved in 650 g of NMP. This redissolved 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 PA-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 34,700.

[Synthesis Example 9]
(Synthesis of polyamide PA-2)
In a separable flask having a volume of 2 liters, AIPA-MO obtained in Synthesis Example 1 was 80.71 g (0.24 mol), AIPA-NBI obtained in Synthesis Example 4 was 19.64 g (0.06 mol), pyridine. 71.2 g (0.9 mol) and 400 g of GBL were added and mixed. Thereafter, the same operation as in Synthesis Example 8 was performed to obtain polyamide PA-2. The polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 29,500.

[Synthesis Example 10]
(Synthesis of polyamide PA-3)
80.71 g (0.24 mol) of AIPA-MO obtained in Synthesis Example 1, 15.49 g (0.06 mol) of diphenyl ether-4,4′-dicarboxylic acid, 71.2 g (0.9 mol) of pyridine, 400 g of GBL was added and mixed, and cooled to 5 ° C. with an ice bath. 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 121.1 g of bis [4- (4-aminophenoxy) phenyl] sulfone. A solution prepared by dissolving (0.28 mol) in 168 g of NMP was added dropwise over about 20 minutes, and the ice bath was removed for 3 hours while maintaining the temperature below 5 ° C. in an ice bath, followed by stirring at room temperature for 5 hours. Thereafter, the same operation as in Synthesis Example 8 was performed to obtain polyamide PA-3. The polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 32,000.

[Synthesis Example 11]
(Synthesis of polyamide PA-4)
A polyamide PA was prepared in the same manner as in Synthesis Example 8 except that “BAPB 103.16 g (0.28 mol)” in Synthesis Example 8 was replaced with “4,4′-diaminodiphenyl ether 56.07 g (0.28 mol)”. -4 was obtained. The polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 30,300.

[Synthesis Example 12]
(Synthesis of polyamide PA-5)
Similar to Synthesis Example 8, except that “BAPB 103.16 g (0.28 mol)” in Synthesis Example 8 was replaced with “2,2′-dimethyl-4,4′-diaminobiphenyl 55.19 g (0.26 mol)”. As a result, polyamide PA-5 was obtained. The polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 23,600.

[Synthesis Example 13]
(Synthesis of polyamide PA-6)
In a separable flask having a capacity of 2 liters, 84.08 g (0.25 mol) of AIPA-MO obtained in Synthesis Example 1, 101.35 g (0.75 mol) of 1-hydroxybenzotriazole, and 39.6 g of pyridine ( 0.5 mol), 5.6 g (0.05 mol) of 4-dimethylaminopyridine and 275 g of N, N-dimethylformamide were added and mixed, and cooled to 5 ° C. in an ice bath. A solution obtained by dissolving and diluting 134.11 g (0.65 mol) of DCC in 134 g of N, N-dimethylformamide was added dropwise over about 20 minutes under ice-cooling. Subsequently, while maintaining cooling in an ice bath, 5 Stirring was continued for hours. Thereafter, 48.81 g (0.232 mol) of 4,4′-methylenebis (cyclohexylamine) dissolved in 146 g of N, N-dimethylformamide was added over about 20 minutes, and the temperature was kept below 5 ° C. in an ice bath. However, the ice bath was removed and the mixture was stirred at room temperature for 10 hours.

Thereafter, the DCU precipitated in the polycondensation process is filtered off under pressure, and while stirring the filtrate (polymer solution), a mixed solution of 1,000 g of water and 4,000 g of isopropanol is added dropwise to separate the precipitated polymer. And redissolved in 800 g of NMP. This re-dissolved solution was dropped into 5 liters of ion-exchanged water with stirring to disperse and precipitate the polymer, recovered, washed with water, and then vacuum dried at 40 ° C. for 48 hours to obtain polyamide PA-6. . The polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 32,600.

[Synthesis Example 14]
(Synthesis of polyamide PA-7)
Into a 1 liter separable flask, 47.9 g (0.2 mol) of AIPA-BA obtained in Synthesis Example 2, 31.6 g (0.4 mol) of pyridine, and 147 g of NMP were charged and mixed, and then an ice bath At 5 ° C. A solution obtained by dissolving 83.4 g (0.404 mol) of DCC in 83 g of NMP was added dropwise over about 20 minutes under ice cooling, followed by 2,2-bis- (3-amino-4-hydroxyphenyl). ) A solution obtained by dissolving 68.1 g (0.19 mol) of hexafluoropropane in 204 g of NMP was added over about 20 minutes, maintained for 3 hours while maintaining the temperature below 5 ° C. in an ice bath, and then removed from the ice bath at room temperature for 10 hours. Stir for hours.

Thereafter, the DCU precipitated in the polycondensation process is filtered off under pressure, and while stirring the filtrate (polymer solution), a mixture of 760 g of water and 190 g of isopropanol is added dropwise to separate the precipitated polymer. Redissolved. This redissolved solution was dropped into 3 liters of ion-exchanged water with stirring to disperse and precipitate the polymer, recovered, washed with water, and then vacuum-dried at 40 ° C. for 48 hours to obtain polyamide PA-6. . The polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 12,600.

[Synthesis Example 15]
(Synthesis of polyamide PA-8)
Into a 2 liter separable flask, 114.11 g (0.3 mol) of AIPA-ME obtained in Synthesis Example 3, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were added and mixed. The same operation as in Synthesis Example 8 was performed to obtain polyamide PA-8. The polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 33,000.

[Synthesis Example 16]
(Synthesis of polyamide PA-9)
“BAPB 103.16 g (0.28 mol)” in Synthesis Example 8 was replaced with “4,4′-diaminodiphenyl ether 28.04 g (0.14 mol) and 2,2′-dimethyl-4,4′-diaminobiphenyl 29.72 g. Except for the replacement with (0.14 mol), the same operation as in Synthesis Example 8 was performed to obtain polyamide PA-9. The polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 28,200.

[Synthesis Example 17]
(Synthesis of polyamide PA-10)
Synthetic Example 8 except that “BAPB 103.16 g (0.28 mol)” in Synthetic Example 8 was replaced with “BAPB 92.85 g (0.252 mol) and 1,8-diaminooctane 4.04 g (0.028 mol)”. The same operation was performed to obtain polyamide PA-10. The polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 26,800.

[Synthesis Example 18]
(Synthesis of polyamide PA-11)
Into a separable flask having a volume 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 an ice bath At 5 ° C. A solution obtained by dissolving 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 2,2-bis [4- (4-aminophenoxy) phenyl]. A solution obtained by dissolving 103.45 g (0.252 mol) of propane in 168 g of NMP was added dropwise over about 20 minutes, and the mixture was stirred at room temperature for 5 hours after removing the ice bath while maintaining the temperature below 5 ° C. in an ice bath. did. Subsequently, a mixture of 36.4 g of a trade name KF-8010 made by Shin-Etsu Chemical Co., Ltd., which is an amino group-modified polydimethylsiloxane at both ends, and 40 g of diethylene glycol dimethyl ether were added dropwise, and the mixture was further stirred at room temperature for 5 hours. Thereafter, the same operation as in Synthesis Example 8 was performed to obtain polyamide PA-11. The polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 28,000.

[Synthesis Example 19]
(Synthesis of polyamide PA-12)
Into a separable flask having a volume of 2 liters, 74.77 g (0.3 mol) of AIPA-MA obtained in Synthesis Example 5, 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 56.07 g (0.28 mol) of 4,4′-diaminodiphenyl ether with 168 g of NMP. The solution dissolved in was added dropwise over about 20 minutes, and the ice bath was removed for 3 hours while maintaining the temperature below 5 ° C., and then the ice bath was removed and the mixture was stirred at room temperature for 5 hours. Thereafter, the same operation as in Synthesis Example 8 was performed to obtain polyamide PA-12. The polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 29,500.

[Synthesis Example 20]
(Synthesis of polyamide PA-13)
In a separable flask having a volume of 2 liters, 70.62 g (0.21 mol) of AIPA-MO, 14.95 g (0.09 mol) of isophthalic acid, 71.2 g (0.9 mol) of pyridine, and 400 g of GBL were charged. Thereafter, the same operation as in Synthesis Example 8 was performed to obtain polyamide PA-13. The polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 32,100.

[Synthesis Example 21]
(Synthesis of polyamide PA-14)
In a separable flask having a volume of 2 liters, AIPA-MO 60.53 g (0.18 mol), diphenyl ether-4,4′-dicarboxylic acid 30.99 g (0.12 mol), and pyridine 71.2 g (0.9 mol). ), 400 g of GBL was added and mixed, and thereafter, the same operation as in Synthesis Example 8 was performed to obtain polyamide PA-14. The polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 30,900.

[Synthesis Example 22]
(Synthesis of polyimide precursor PI-1)
In a separable flask having a volume of 5 L, 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 were added. , 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, followed by 185.97 g (0.93 mol) of 4,4′-diaminodiphenyl ether. What was disperse | distributed to 650 g of GBL was added over about 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, A polyimide precursor PI-1 was obtained. The polystyrene-equivalent GPC weight average molecular weight measured under the same conditions as in Synthesis Example 8 was 29,000.

[Example 1]
To 100 parts by mass of the polyamide PA-1 obtained in Synthesis Example 8, 190 parts by mass of NMP was added to dissolve the polyamide PA-1 to prepare a crude solution. This was a PTFE filter having a pore size of 0.2 microns. To obtain a resin solution V-1.

[Example 2]
The crude solution in Example 1 was filtered in the same manner as in Example 1 except that 5 parts by mass of 1,3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime was further added as a photopolymerization initiator. A resin composition solution V-2 was obtained.

[Example 3]
Filtration was performed in the same manner as in Example 1 except that 8 parts by mass of tetraethylene glycol dimethacrylate as a photopolymerizable monomer was further added to the crude solution in Example 2 to obtain a resin composition solution V-3.

[Example 4]
Filtration was performed in the same manner as in Example 1 except that 5 parts by mass of hexamethoxymethylated melamine as a thermal crosslinking agent was further added to the crude solution in Example 3, to obtain a resin composition solution V-4.

[Example 5]
In the crude solution of Example 4, 5 parts by mass (1 part by mass as a pure component of S-1) of a 20% by mass NMP solution of the silane coupling agent S-1 obtained in Synthesis Example 6 was obtained. 10 parts by mass of a 20% by mass NMP solution of the silane coupling agent S-2 obtained in the above (2 parts by mass as a pure component of S-2), and 5 parts by mass of 3- (trialkoxysilyl) propylsuccinic anhydride A resin composition solution V-5 was obtained by filtration in the same manner as in Example 1 except for adding a part.

[Example 6]
Filtration was performed in the same manner as in Example 1 except that 2 parts by mass of 5-carboxybenzotriazole was further added to the crude solution in Example 5, to obtain a resin composition solution V-6.

[Example 7]
100 parts by mass of the polyamide PA-1 obtained in Synthesis Example 8 is 5 parts by mass of 1,3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime, 8 parts by mass of tetraethylene glycol dimethacrylate, 5 parts by mass of hexamethoxymethylated melamine, 5 parts by mass of a 20% by mass NMP solution of the silane coupling agent S-1 obtained in Synthesis Example 6 {1 part by mass as the pure content of S-1}, Synthesis Example 7 10 parts by mass of a 20% by mass NMP solution of the silane coupling agent S-2 obtained in Step 2 (2 parts by mass as a pure component of S-2) and 5 parts by mass of 3- (trialkoxysilyl) propylsuccinic anhydride 2 parts by mass of 5-carboxybenzotriazole, 5 parts by mass of N, N-bis (2-hydroxyethyl) aniline, and 0.05 parts by mass of N-nitrosodiphenylamine , Dissolved in NMP190 parts by weight was filtered through a PTFE filter having a pore size of 0.2 micron to obtain a resin composition solution V-7.

[Example 8]
Polyamide PA-1 used in Example 7 was replaced with PA-2 obtained in Synthesis Example 9, and 3- (trialkoxysilyl) propyl succinic anhydride used in Example 7 was replaced with 3 Resin composition solution V-8 was obtained in the same manner as in Example 7 except that it was replaced with glycidoxypropyl (dimethoxy) methylsilane.

[Example 9]
Polyamide PA-1 used in Example 7 was replaced with PA-3 obtained in Synthesis Example 10, and 3- (trialkoxysilyl) propyl succinic anhydride used in Example 7 was replaced with 3 -Resin composition solution V-9 was obtained in the same manner as in Example 7 except that it was replaced with isocyanatopropyltriethoxysilane.

[Examples 10 to 17]
Resin composition solution V- was prepared in the same manner as in Example 7, except that polyamide PA-1 used in Example 7 was replaced with polyamide PA-4 to PA-11 obtained in Synthesis Examples 11 to 18, respectively. 10 to V-17 were obtained.

[Comparative Examples 1 to 3]
Resin composition solution V ′ was obtained in the same manner as in Example 7, except that the polyamide PA-1 used in Example 7 was replaced with the polyamide PA-12 to PA-14 obtained in Synthesis Examples 19 to 21, respectively. -1 to V'-3 were obtained.

[Comparative Example 4]
Except that the polyamide PA-1 used in Example 7 was replaced with the polyimide precursor PI-1 obtained in Synthesis Example 22 and the amount of solvent NMP used was 165 parts by mass, the same as Example 7 was performed. Resin composition solution V′-4 was obtained.

Note: Figures in parentheses in the table represent mol%. Abbreviations not defined above are as follows.
ODPA: diphenyl ether-3,3 ′, 4,4′-tetracarboxylic dianhydride DEDC: diphenyl ether-4,4′-dicarbonyl dichloride DEDA: diphenyl ether-4,4′-dicarboxylic acid IPA: isophthalic acid BAPB: 4 , 4′-bis (4-aminophenoxy) biphenyl BAPS: bis [4- (4-aminophenoxy) phenyl] sulfone DADPE: 4,4′-diaminodiphenyl ether mTB: 2,2′-dimethyl-4,4′- Diaminobiphenyl MBCA: 4,4'-methylenebis (cyclohexylamine)
6FAP: 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane ODA: 1,8-octanediamine BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane

Evaluation of Photosensitive Properties and Adhesion during Development Using the resin composition solutions of Examples 2 to 17 and Comparative Examples 1 to 4 with a 6 inch silicon wafer using a spin coater (manufactured by Tokyo Electron, model name: Clean Track Mark 8) The film was applied on top and prebaked at 95 ° C. for 4 minutes to obtain a coating film having an initial film thickness of 10 microns. The coatings, i-line stepper exposing machine (manufactured by Nikon, model name NSR2005i8A) by, through evaluation photomask, exposure was stepwise changed by 50 mJ / cm ² in the range of 100 ~ 1100mJ / cm ² exposure did.

30 minutes after exposure, for coating films other than Example 13, using cyclopentanone as a developer, the time until the unexposed area completely dissolves and disappears is multiplied by 1.4. And then, spray rinsing with propylene glycol monomethyether acetate for 10 seconds to obtain a relief pattern made of a resin film. For the coating film of Example 13, 30 minutes after exposure, a 2.38% aqueous solution of tetramethylammonium hydroxide (product number AZ-300MIF, manufactured by AZ Electronic Materials) was used as a developer, and the unexposed area was completely Paddle development was performed by multiplying the time until dissolution disappeared by 1.4 by a time period, followed by rotary stream rinsing with ion-exchanged water to obtain a relief pattern made of a resin film.

The obtained relief pattern is visually observed under an optical microscope, and the minimum exposure (sensitivity) to obtain a sharp pattern without swelling, the dimension of the via hole (rectangular concave pattern) at the time of irradiation with the minimum exposure (resolution) Then, the adhesion to the substrate (pattern floating and peeling) was evaluated. The results are shown in Table 2 below.

Evaluation of Mechanical Properties The resin composition solutions of Examples 1 to 17 and Comparative Examples 1 to 4 were applied to a 6-inch silicon wafer on which an aluminum thin film had been vacuum-deposited in the same manner as in the evaluation of the photosensitive characteristics described above. After coating and pre-baking, a vertical curing furnace (manufactured by Koyo Lindberg, model name: VF-2000B) was subjected to heat curing treatment at 180 ° C. for 2 hours in a nitrogen atmosphere, and a cured resin film having a thickness of 10 μm was formed. Produced. This resin film is cut to a width of 3.0 mm using a dicing saw (manufactured by Disco, model name DAD-2H / 6T), immersed in a 10% hydrochloric acid aqueous solution and peeled off from the silicon wafer, and a strip-shaped film sample It was. This film sample was left in an atmosphere of 23 ° C. and 55% RH for 24 hours or more, and then a tensile test with Tensilon according to ASTM D-882-88 was performed to evaluate the elongation of the film sample. The results are shown in Table 2 below.

Evaluation of heat resistance Using a thermomechanical analyzer (manufactured by Shimadzu Corporation, model name TMA-50), the glass transition temperature (Tg) of the film sample prepared for evaluation of the mechanical properties was measured, and the heat resistance of the resin film was measured. It was used as an index. The measurement conditions are a sample length of 10 mm, a constant load of 200 g / mm ² , a measurement temperature range of 25 ° C. to 450 ° C., a temperature increase rate of 10 ° C./min, and a nitrogen atmosphere. The results are shown in Table 2 below.

Evaluation of Residual Stress The resin composition solutions of Examples 1 to 17 and Comparative Examples 1 to 4 were applied to the above-mentioned photosensitive characteristics on a 6-inch silicon wafer having a thickness of 625 μm ± 25 μm for which the “warping amount” had been measured in advance. After applying and pre-baking under the same conditions as in the evaluation of the above, after curing using a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B) at 180 ° C. for 2 hours in a nitrogen atmosphere A silicon wafer with a resin film having a thickness of 10 μm was produced. The residual stress of the wafer was measured using a residual stress measuring device (manufactured by Tencor, model name FLX-2320). The results are shown in Table 2 below.

Evaluation of chemical resistance The resin composition solutions of Examples 1 to 17 and Comparative Examples 1 to 4 were previously prepared with a 3-aminopropyltriethoxysilane using a spin coater (manufactured by Tokyo Electron, model name: Clean Track Mark 8). The film was coated on a 6-inch silicon wafer that had been surface-treated in step 1, and prebaked at 95 ° C. for 4 minutes to obtain a coating film having an initial film thickness of 10 microns.

This coating film was exposed with an i-line stepper exposure machine (manufactured by Nikon, model name NSR2005i8A) under conditions of a constant exposure amount through a photomask for evaluation. The exposure amount was set by adding 200 mJ / cm ² to each minimum exposure amount (sensitivity) at which a sharp pattern without swelling was obtained in the above-described evaluation of the photosensitive characteristics.

30 minutes after exposure, for coating films other than Example 1 and Example 13, using cyclopentanone as the developer, the time until the unexposed part completely dissolves and disappears is multiplied by 1.4 Was followed by rotary spray rinsing with propylene glycol monomethyl ether acetate for 10 seconds to obtain a relief pattern comprising a resin film. For the coating film of Example 13, 30 minutes after exposure, a 2.38% aqueous solution of tetramethylammonium hydroxide (product number AZ-300MIF, manufactured by AZ Electronic Materials) was used as a developer, and the unexposed area was completely Paddle development was performed by multiplying the time until dissolution disappeared by 1.4 by a time period, followed by rotary stream rinsing with ion-exchanged water to obtain a relief pattern made of a resin film.

The coating film of Example 1 was not developed because the coating film had no photosensitivity.

The obtained relief pattern film (undeveloped flat film in Example 1) was heat-cured at 180 ° C. for 2 hours in a nitrogen atmosphere using a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B). The cured relief pattern film (cured flat film in Example 1) was produced.

These cured films were formed on a resist stripping solution {product of ATMI, product name ST-44, main components: 2- (2-aminoethoxy) ethanol, 1-cyclohexyl-2-pyrrolidone} heated to 85 ° C. for 5 minutes. It was immersed, allowed to cool, washed with running water for 1 minute, and air dried. Thereafter, the surface of the film is visually observed under an optical microscope, and the presence or absence of damage due to chemicals such as cracks and roughness, and the rate of change in film thickness before and after chemical treatment (unit%. 100% is no change in film thickness. 100% or more. Was swelled, and less than 100% dissolved in the film). The results are shown in Table 3 below.

Evaluation of copper discoloration after curing The resin composition solutions of Examples 2 to 17 and Comparative Examples 1 to 4 were applied to a 6-inch silicon wafer using a spin coater (manufactured by Tokyo Electron, model name: Clean Track Mark 8). Titanium was vacuum-deposited and copper was further vacuum-deposited on top of the substrate that had been pretreated with 3-aminopropyltriethoxysilane, pre-baked at 95 ° C for 4 minutes, and an initial film thickness of 10 microns. A coating film was obtained.

This coating film was exposed with an i-line stepper exposure machine (manufactured by Nikon, model name NSR2005i8A) under conditions of a constant exposure amount through a photomask for evaluation. The exposure amount was set by adding 200 mJ / cm ² to each minimum exposure amount (sensitivity) at which a sharp pattern without swelling was obtained in the above-described evaluation of the photosensitive characteristics.

30 minutes after exposure, for coating films other than Example 13, using cyclopentanone as a developer, the time until the unexposed area completely dissolves and disappears is multiplied by 1.4. And then, spray rinsing with propylene glycol monomethyether acetate for 10 seconds to obtain a relief pattern made of a resin film. For the coating film of Example 13, 30 minutes after exposure, a 2.38% aqueous solution of tetramethylammonium hydroxide (product number AZ-300MIF, manufactured by AZ Electronic Materials) was used as a developer, and the unexposed area was completely Paddle development was performed by multiplying the time until dissolution disappeared by 1.4 by a time period, followed by rotary stream rinsing with ion-exchanged water to obtain a relief pattern made of a resin film.

The relief pattern on the obtained copper substrate was heat-cured (cured) at 180 ° C. for 2 hours in a nitrogen atmosphere using a vertical curing furnace (manufactured by Koyo Lindbergh, model name VF-2000B) to obtain a copper A cured relief pattern on the substrate was prepared. The copper substrate surface of the unexposed part was visually observed under an optical microscope, and the presence or absence of discoloration of the copper surface after curing was evaluated. The results are shown in Table 3 below.

In Examples 1 to 17, excellent chemical resistance is achieved even at low temperature curing of 180 ° C. At the same time, high mechanical properties exhibiting an elongation of 50% or higher, excellent heat resistance exhibiting a Tg of 200 ° C. or higher, low residual stress characteristics of 25 MPa or lower, and a polyamide resin having unprecedented excellent low-temperature curing characteristics And the photosensitive resin composition containing this can be provided.
Further, in Examples 3 to 17, excellent photosensitivity can be obtained, and in Examples 4 to 17, excellent heat resistance can be obtained. Further, in Examples 5 to 17, excellent adhesion during development can be obtained. Further, in Examples 6 to 17, discoloration of the copper surface after curing could be suppressed.

On the other hand, Comparative Example 1 is a case in which a polyamide resin made from a raw material made of a material in which a methacrylic group is directly linked to an amino group of AIPA and a radically polymerizable unsaturated bond group is introduced by a methacrylamide structure (AIPA-MA) is used. However, because of the low degree of freedom of the unsaturated bond group, the photosensitivity is greatly inferior to the examples, and at the same time, the chemical resistance is also greatly inferior to the examples.

Comparative Examples 2 and 3 are cases where the copolymerization ratio of a radically unsaturated unsaturated group introduced into the amino group of AIPA (eg, AIPA-MO) is below the preferred range of the present invention. The chemical resistance is also greatly inferior to that of the Examples, probably due to the decrease in the structure derived from AIPA, at the same time as the deterioration of the photosensitive characteristics due to the decrease in the radical polymerizable unsaturated bond group.

Comparative Example 4 is a case where a resin film made of a conventional photosensitive polyimide precursor composition is cured at a low temperature of 180 ° C., but imidization is incomplete, mechanical properties, heat resistance, residual stress, In any point of chemical resistance, it is remarkably inferior to the examples.

The photosensitive resin composition of the present invention and the polyamide resin used therefor are insulating materials for electronic components, surface protective films for semiconductor devices, interlayer insulating films, heat resistant coatings such as α-ray shielding films, and image sensors, It is suitable as a photosensitive resin composition used for forming a heat-resistant coating film in a semiconductor device or the like equipped with a micromachine or a microactuator.

Claims (16)

Following formula (1):

{Wherein X is a trivalent organic group having 6 to 15 carbon atoms, m is 0 or 2, and Y is a divalent organic group having 6 to 35 carbon atoms when m = 0, When m = 2, it is a tetravalent organic group having 6 to 35 carbon atoms, and R ₁ is a radically polymerizable unsaturated bond group having 5 to 20 carbon atoms, which may contain atoms other than carbon. It is an aliphatic group having at least one. Are included so that the number of repetitions is in the range of 2 to 150 and the number of repetitions is in the range of 80 to 100% of the total number of all the structural units constituting the polyamide resin. Following formula (2):

{Wherein X is a trivalent organic group having 6 to 15 carbon atoms, m is 0 or 2, and Y is a divalent organic group having 6 to 35 carbon atoms when m = 0, When m = 2, it is a tetravalent organic group having 6 to 35 carbon atoms, W is a divalent organic group having 6 to 15 carbon atoms, k is an integer of 1 or more, and (n + k) Is an integer of 5 to 150, and R ₁ is an aliphatic group having 5 to 20 carbon atoms which may contain atoms other than carbon and has at least one radical-polymerizable unsaturated bond group. } The polyamide resin containing the structure represented by the formula (2) so that the repeating number n in the formula (2) is 80% or more of the total number of all the structural units constituting the polyamide resin. Following formula (3):

{Wherein X is a trivalent organic group having 6 to 15 carbon atoms, m is 0 or 2, and Y is a divalent organic group having 6 to 35 carbon atoms when m = 0, When m = 2, it is a tetravalent organic group having 6 to 35 carbon atoms, W is a divalent organic group having 6 to 15 carbon atoms, l is 0 or an integer of 1 or more, and ( n + 1) is an integer of 2 to 150, and R ₁ is an aliphatic group having 5 to 20 carbon atoms which may contain atoms other than carbon and which has at least one radical-polymerizable unsaturated bond group. . }, A polyamide resin in which the repeating unit n in the formula (3) is in the range of 80 to 100% of the total number of all the structural units constituting the polyamide resin. R ₁ is represented by the following formula (4):

{In the formula, R ₂ is a C 4-19 aliphatic group having at least one radical-polymerizable unsaturated bond group. The polyamide resin according to any one of claims 1 to 3, which is a group represented by The polyamide resin according to any one of claims 1 to 3, wherein R ₁ is a group having at least one (meth) acryloyloxymethyl group. The W, X, and Y are each independently a group selected from the group consisting of an aromatic group, an alicyclic group, an aliphatic group, a siloxane group, and a group of a composite structure thereof. The polyamide resin according to any one of the above. A photosensitive resin composition comprising (A) 100 parts by mass of the polyamide resin according to any one of claims 1 to 6, and (B) 0.5 to 20 parts by mass of a photopolymerization initiator. The photosensitive resin composition according to claim 7, further comprising (C) a monomer having a photopolymerizable unsaturated bond group in an amount of 1 to 40 parts by mass with respect to 100 parts by mass of the polyamide resin of (A). (D) A heat-crosslinkable compound is further included in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the polyamide resin (A), and the (D) heat-crosslinkable compound heats the polyamide resin (A). The photosensitive resin composition according to claim 7 or 8, wherein the photosensitive resin composition is a compound to be crosslinked or a compound that itself forms a thermal crosslinking network. The photosensitive resin composition according to claim 9, wherein the (D) thermally crosslinkable compound has an alkoxymethyl group as a thermally crosslinkable group. The photosensitive resin composition according to any one of claims 7 to 10, further comprising (E) a silane coupling agent in an amount of 0.1 to 25 parts by mass with respect to 100 parts by mass of the polyamide resin (A). object. The photosensitive resin composition according to claim 11, wherein the (E) silane coupling agent is an organosilicon compound having a (dialkoxy) monoalkylsilyl group or a (trialkoxy) silyl group. The photosensitive resin composition according to any one of claims 7 to 12, further comprising (F) a benzotriazole-based compound in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyamide resin of (A). object. A photosensitive resin composition solution comprising the photosensitive resin composition according to any one of claims 7 to 13 and a solvent. A photosensitive resin composition according to any one of claims 7 to 13 or a photosensitive resin composition solution according to claim 14 is applied on a substrate to form a coating film of the photosensitive resin composition. The process of
An exposure step of irradiating the coating film with actinic rays directly or through a patterning mask;
A development method of forming a relief pattern by dissolving and removing unexposed portions of the coating film using a developer, and a method of forming a relief pattern by heating and curing the relief pattern . A semiconductor device having a cured relief pattern formed by the method for forming a cured relief pattern according to claim 15.