KR20100063748A - 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 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, 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 Rrepresents 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, formation method of hardening relief pattern, and semiconductor device {POLYAMIDE RESIN, PHOTOSENSITIVE RESIN COMPOSITION, METHOD FOR FORMING CURED RELIEF PATTERN, AND SEMICONDUCTOR DEVICE}

선 차폐막 등의 내열성 도포막, 및 이미지 센서, 마이크로 머신 또는 마이크로 엑추에이터를 탑재한 반도체 장치 등에 사용할 수 있는 폴리아미드 수지, 그 폴리아미드 수지를 함유하는 감광성 수지 조성물, 그 감광성 수지 조성물을 사용한 경화 릴리프 패턴의 형성 방법, 그리고 그 경화 릴리프 패턴을 갖는 반도체 장치에 관한 것이다. 더욱 상세하게는, 본 발명은 자외선 노광시의 감광 특성이 우수하고, 예를 들어 200 ℃ 이하의 가열 경화 조건에서도 우수한 내열성, 내약품성, 기계 특성, 및 저잔류 응력 특성을 나타내는, 신규 감광성 폴리아미드 수지, 및 이것을 함유하는 감광성 수지 조성물, 그리고 그 감광성 수지 조성물을 사용하여 제조되는 반도체 장치에 관한 것이다. The present invention provides an insulating material for electronic components, a surface protective film of a semiconductor device, an interlayer insulating film,

Heat-resistant coating films, such as a line shielding film, and polyamide resin which can be used for a semiconductor device equipped with an image sensor, a micromachine, or a micro actuator, the photosensitive resin composition containing this polyamide resin, and the hardening relief pattern using the photosensitive resin composition And a semiconductor device having the cured relief pattern. More specifically, the present invention is a novel photosensitive polyamide which is excellent in photosensitivity during ultraviolet exposure and exhibits excellent heat resistance, chemical resistance, mechanical properties, and low residual stress properties even under heat curing conditions of, for example, 200 ° C. or less. It relates to a resin and a photosensitive resin composition containing the same, and a semiconductor device manufactured using the photosensitive resin composition.

선 차폐막 등의 용도로는, 우수한 내열성, 전기 특성 및 기계 특성을 겸비하는 폴리이미드 수지가 널리 사용되고 있다. 이 수지는, 통상, 감광성 폴리이미드 전구체 조성물의 형태로 제공되며, 이것을 기재에 도포하여, 원하는 패터닝 마스크를 개재하여 활성 광선을 조사 (노광) 하고, 현상하여, 가열 경화 (열이미드화) 처리함으로써, 내열성의 폴리이미드 수지로 이루어지는 릴리프 패턴을 용이하게 형성시킬 수 있다는 특징을 갖고 있다 (예를 들어, 이하의 특허문헌 1 을 참조할 것). Insulating materials for electronic components, and surface protective films of semiconductor devices, interlayer insulating films, and

As applications for sunscreens and the like, polyimide resins having excellent heat resistance, electrical characteristics, and mechanical characteristics are widely used. This resin is usually provided in the form of a photosensitive polyimide precursor composition, which is applied to a base material, irradiated (exposured) the actinic light through a desired patterning mask, and developed, followed by heat curing (thermal imidization) treatment. This has the characteristic that the relief pattern which consists of heat-resistant polyimide resin can be formed easily (for example, refer the following patent document 1).

In recent years, in the manufacturing process of a semiconductor device, although the demand for the material which can perform a heat hardening (thermal imidation) process at a lower temperature mainly increases on the basis of the material of a structural member, and a structural design, the prior art In the case of the polyimide resin precursor composition, when the heat curing treatment temperature is lowered, heat imidation cannot be completed, and various physical properties deteriorate, so the lower limit of the heat curing treatment temperature is only about 300 ° C.

Although measures to reduce the heat curing temperature have been made by research of the polymer skeleton structure and the composition additive, in order to maintain the practical polyimide membrane properties, the 250 degreeC degree is considered to be a limit (for example, the following patent document) 2).

Therefore, the photosensitive resin composition which is excellent in the photosensitive characteristic at the time of ultraviolet exposure, and shows the film characteristic suitable for practical use also in the heat-hardening conditions of 200 degrees C or less is not known in the art.

Japanese Unexamined Patent Publication No. 6-342211 Japanese Laid-Open Patent Publication 2003-316002 Japanese Laid-Open Patent Publication No. 63-182322 International Publication No. 2006/008991

Patent Literature 3 discloses a polyamide in which a photosensitive group is directly bonded to a resin skeleton via an amide group, while Patent Literature 4 discloses a polyimideamide, but any technique is more effective than heat curing (thermal imidization) treatment. When carried out at low temperatures, it was not suitable for practical use. The problem to be solved by the present invention is a poly which is excellent in chemical resistance and resolution, and has excellent film resistance to the resin film even when the resin film is formed under low temperature heat curing conditions such as 200 ° C. or lower. It is to provide an amide resin and a photosensitive resin composition. Moreover, also providing the semiconductor device which has the hardening relief pattern formed by the method and the formation method of the hardening relief pattern using this photosensitive resin composition is a subject which this invention is trying to solve.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, as a result of earnestly examining, it discovered that the said subject can be solved by manufacturing the photosensitive resin composition based on the polyamide manufactured from the specific raw material, and came to complete this invention. . Specifically, the present invention is as follows [1] to [16]:

[1] the following formula (1):

[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, and a carbon number when m = 2 It is a tetravalent organic group which is 6-35, R <_1> is the aliphatic group which has at least one C5-C20 radically polymerizable unsaturated bond group which may contain atoms other than carbon}, and repeats The polyamide resin which contains so that the repeating number may be in the range of 80 to 100% of the total number of all the structural units which comprise a polyamide resin within the range of numbers 2-150.

[2] the following formula (2):

[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, and a carbon number when m = 2 and 6-35 of the tetravalent organic group, W is a carbon atoms, and 6-15 divalent organic group, and k is an integer of 1 or more, at the same time (n + k) is an integer in the range of 5 ~ 150, R ₁ is other than carbon Repeating number n in said Formula (2) makes the structure shown by the structure represented by the}} which is a C5-C20 aliphatic group which has at least 1 radically polymerizable unsaturated bond group which may contain the atom of the whole. The polyamide resin contained so that it may be 80% or more of the total number of structural units.

[3] the following formula (3):

(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, and a carbon number when m = 2 Is a tetravalent organic group having 6 to 35, W is a divalent organic group having 6 to 15 carbon atoms, l is 0 or an integer of 1 or more, and at the same time (n + l) is an integer of 2 to 150, R ₁ is Only the structure represented by the C5-C20 aliphatic group which has at least 1 radically polymerizable unsaturated bond group which may contain atoms other than carbon as a structural unit, and repeating number n in said Formula (3) is poly The polyamide resin in 80 to 100% of the total number of all the structural units which comprise an amide resin.

[4] wherein R ₁ is the following Formula (4):

[Formula 4]

The polyamide resin in any one of said [1]-[3] which is group represented by {In formula, R <_2> is a C4-C19 aliphatic group which has at least 1 radically polymerizable unsaturated bond group.

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

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

[7] (A) 100 parts by mass of the polyamide resin according to any one of the above [1] to [6], and

(B) Photosensitive resin composition containing 0.5-20 mass parts of photoinitiators.

[8] The photosensitive resin composition according to the above [7], further comprising (C) a monomer having a photopolymerizable unsaturated bond group at 1 to 40 parts by mass with respect to 100 parts by mass of the polyamide resin of the above (A).

[9] The (D) thermally crosslinkable compound is further contained in an amount of 1 to 20 parts by mass based on 100 parts by mass of the polyamide resin of the above (A), and the (D) thermally crosslinkable compound contains the polyamide resin of the above (A). The photosensitive resin composition as described in said [7] or [8] which is a compound which thermally crosslinks, or is a compound which forms a thermal crosslinking network itself.

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

[11] The photosensitive resin composition according to any one of the above [7] to [10], further comprising (E) a silane coupling agent at 0.1 to 25 parts by mass with respect to 100 parts by mass of the polyamide resin of (A).

[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 photosensitive resin composition according to any one of the above [7] to [12], further comprising (F) a benzotriazole compound at 0.1 to 10 parts by mass relative to 100 parts by mass of the polyamide resin of the above (A). .

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

[15] a step of applying 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] to form a coating film of the photosensitive resin composition,

An exposure step of irradiating actinic light directly on the coating film or via a patterning mask;

A developing step of forming a relief pattern by dissolving and removing unexposed portions of the coating film using a developing solution, and

A method of forming a cured relief pattern, comprising the step of heating and curing the relief pattern to form a cured relief pattern.

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

The polyamide resin of this invention and the photosensitive resin composition containing this can provide the resin film which shows the outstanding chemical-resistance even in low-temperature heat-hardening conditions like 200 degrees C or less, for example. The present invention also provides a method of 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 described in detail. In addition, in each formula described in this specification, 1 type may be sufficient as the structure represented by the same code | symbol, when two or more exist in a molecule, and a combination of 2 or more types may be sufficient, respectively.

<Polyamide resin>

In one aspect, the present invention provides the following formula (1):

[Chemical Formula 5]

{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, and a carbon number when m = 2 It is a tetravalent organic group which is 6-35, R <_1> is the aliphatic group which has at least one C5-C20 radically polymerizable unsaturated bond group which may contain atoms other than carbon}, and repeats The polyamide resin is contained in the range of the number 2-150, and the repeating number is contained in 80 to 100% of the total number of all the structural units which comprise a polyamide resin.

In this aspect, the repeating number of the structural unit represented by said Formula (1) in 1 molecule of polyamide resins is 2-150, and if it is 2 or more, the requirement as a polymer which this invention expects is satisfied, and if it is 150 or less, it will be photosensitive. It is preferable at the point of the solubility with respect to the dilution solvent at the time of making a resin composition, the rapidity at the time of image development processing, etc. As for the said repeating number of the structural unit represented by said Formula (1), it is more preferable that it is 2-100. In addition, in this specification, the repeating number of a structural unit means the number of the said structural unit which exists in 1 molecule, and the structural unit may be repeated continuously or may be repeated through another structural unit.

In this aspect, the ratio of the repeating number of the structural unit represented by said Formula (1) in the total number of all the structural units which comprise polyamide resin exists in 80 to 100% of range. When the said ratio is 80% or more, the photosensitive characteristic of the coating film which consists of the photosensitive resin composition of this invention can be improved to the extent which this invention expects, Furthermore, to the mechanical property, heat resistance, and chemical resistance after heat-hardening of the said coating film, Also, it can be made excellent in the grade which this invention expects. It is preferable that the said ratio is 85% or more. Although the structural unit of a polyamide resin may be only the structural unit represented by said Formula (1) from a photosensitive characteristic, heat resistance, and chemical-resistance viewpoint (that is, the said ratio is 100%), the various structure which touches in the process of forming a semiconductor element It is also preferable that the polyamide resin has a structural unit other than the structural unit represented by the above (1) for the purpose of further improving the adhesion to the material, imparting various properties as desired, and in this case, the ratio Is 20% or less, and preferably 15% or less. When the repeating number of the structural unit represented by said formula (1) is 2 and 3, the repeating number becomes 100% of the total number of all the structural units which comprise a polyamide resin.

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

[Formula 6]

{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, and a carbon number when m = 2 and 6-35 of the tetravalent organic group, W is a carbon atoms, and 6-15 divalent organic group, and k is an integer of 1 or more, at the same time (n + k) is an integer in the range of 5 ~ 150, R ₁ is other than carbon Repeating number n in said Formula (2) makes the structure shown by the structure represented by the}} which is a C5-C20 aliphatic group which has at least 1 radically polymerizable unsaturated bond group which may contain the atom of the whole. The polyamide resin containing so that it may become 80% or more of the total number of a structural unit is provided. In said formula (2), the structure of the structure of the repeating number n and the structure of the repeating number k may be random or a block may be sufficient as it.

K in Formula (2) is an integer greater than or equal to 1, and (n + k) is an integer of 5-150 simultaneously. When k is 1 or more, the effect of copolymerizing the various structures represented by repeating number k is acquired. At the same time, when (n + k) is 5 or more, the requirement as a polymer expected by the present invention is satisfied, and when it is 150 or less, in terms of solubility in a diluting solvent when the photosensitive resin composition is used, and rapidity in developing treatment, etc. desirable. It is preferable that (n + k) is 5-100.

In this aspect, the ratio of the number of structural units (that is, n) of repeating number n in the said Formula (2) is 80% or more in the total number of all the structural units which comprise polyamide resin. When the said ratio is 80% or more, the photosensitive characteristic of the coating film which consists of the photosensitive resin composition of this invention can be improved to the extent which this invention expects, Furthermore, it is the mechanical property after heat-hardening of the coating film, heat resistance, and chemical resistance. Also, it can be made excellent in the grade which this invention expects. It is preferable that the said ratio is 85% or more.

In this aspect, the ratio of the number of structural units (that is, k) of the repeating number k in the said Formula (2) is 20% or less in the total number of all the structural units which comprise polyamide resin. When the said ratio is 20% or less, in addition to improving the outstanding photosensitive characteristic, mechanical property, heat resistance, and chemical-resistance of this invention, and simultaneously improving the adhesiveness with the various component materials which contact in the process of forming a semiconductor element, etc. Various characteristics can be given accordingly. It is preferable that the said ratio is 15% or less. The polyamide resin in this aspect may only be a structural unit represented by said Formula (2) from a viewpoint of the photosensitive characteristic, mechanical property, heat resistance, and chemical-resistance which this invention aims at, and said Formula ( You may have structural units other than the structure shown by 2).

When the terminal of the polyamide resin of this invention is a structural unit represented by said Formula (1) or (2), a molecular chain terminal is a carboxyl group derived from dicarboxylic acid containing the trivalent organic group represented by X, or Y Although it is the amino group derived from diamine containing the divalent or tetravalent organic group shown by these, Various chemical modified bodies (for example, an ester body, an amide body, etc.) of the said carboxyl group, and various chemical modified bodies of the said amino group (for example, Amides, urethanes, imides and the like).

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

[Formula 7]

{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, and a carbon number when m = 2 Is a tetravalent organic group having 6 to 35, W is a divalent organic group having 6 to 15 carbon atoms, l is 0 or an integer of 1 or more, and at the same time (n + l) is an integer of 2 to 150, R ₁ is Only the structure represented by the C5-C20 aliphatic group which has at least 1 radically polymerizable unsaturated bond group which may contain atoms other than carbon as a structural unit, and repeating number n in said Formula (3) is poly The polyamide resin which exists in 80 to 100% of the range of all the structural units which comprise an amide resin is provided. In addition, in said Formula (3), the structure of the structure of the repeating number n and the structure of the repeating number l may be random or a block may be sufficient as it.

(N + l) in Formula (3) is 2-150, and when it is 2 or more, the requirement as a polymer which this invention expects is satisfied, and when it is 150 or less, it is the solubility with respect to the diluting solvent at the time of setting it as the photosensitive resin composition, It is preferable at the point of rapidity at the time of image development processing. It is preferable that the said repeating number of the structural unit represented by said Formula (3) is 2-100.

In this aspect, the ratio of the repeating number of the structural unit represented by repeating unit n in the total number of all the structural units which comprise polyamide resin exists in 80 to 100% of range. When the said ratio is 80% or more, the photosensitive characteristic of the coating film which consists of the photosensitive resin composition of this invention can be improved to the extent which this invention expects, Furthermore, also about the mechanical property, heat resistance, and chemical resistance after heat-hardening of the said coating film, The present invention can be made excellent to the extent expected by the present invention. It is preferable that the said ratio is 85% or more. Although the structural unit of a polyamide resin may be sufficient as the structural unit represented by repeating unit n (100% of ratio n) from a photosensitive characteristic, heat resistance, and a chemical-resistance viewpoint, with the various structural materials contacted in the process of forming a semiconductor element, It is also preferable to have a structural unit represented by repeating unit l for the purpose of further improving the adhesiveness of, or providing various characteristics as desired, and in this case, it is preferable that the said ratio is 20% or less and 15% or less. Do. When the structural unit represented by the repeating unit l is 20% or less of the total number of all the structural units, various characteristics as desired can be imparted while securing the photosensitive characteristics, mechanical properties, heat resistance, and chemical resistance achieved by the present invention. Will be. When (n + l) is 2-4, the structural unit represented by the repeating unit n becomes 100% of the total number of all the structural units which comprise a polyamide resin.

The molecular chain terminal of the polyamide resin in this embodiment is a carboxyl group derived from dicarboxylic acid containing a trivalent organic group represented by X, or a carboxyl group derived from dicarboxylic acid containing a divalent organic group represented by W, It is an amino group derived from diamine containing a divalent or tetravalent organic group represented by Y, but various chemical modifiers of the carboxyl group (for example, esters, amides and the like) and various chemical modifiers of the amino group (for example, Amides, urethanes, imides and the like).

In said formula (1)-(3), R <_1> is a C5-C20 aliphatic group which has at least 1 radically polymerizable unsaturated bond group which may contain atoms other than carbon. R ₁ represents the following formula (4) from the viewpoint of photosensitivity, chemical resistance, and the like:

[Formula 8]

It is preferable that it is group represented by {In formula, R <_2> is a C4-C19 aliphatic group which has at least 1 radically polymerizable unsaturated bond group. " Moreover, it is preferable that R <_1> is group which has at least 1 (meth) acryloyl oxymethyl group from a viewpoint of making photosensitive characteristic more excellent.

In said Formula (1)-(3), the trivalent organic group represented by X is a C6-C15 trivalent organic group from a viewpoint of photosensitivity, mechanical property, heat resistance, chemical-resistance, etc. In formulas (1) to (3), the divalent or tetravalent organic group represented by Y is an organic group having 6 to 35 carbon atoms in view of photosensitivity, mechanical properties, heat resistance, chemical resistance, and the like. In addition, in Formula (2) and (3), the divalent organic group represented by W is a bivalent organic group with 6-15 carbon atoms from a viewpoint of photosensitivity, heat resistance, chemical-resistance, etc. W is a structure in which two carboxyl group-derived portions are removed from the structure of a dicarboxylic acid or a derivative thereof.

In the present invention, from the viewpoint of photosensitivity, mechanical properties, heat resistance, chemical resistance, etc., each of W, X, and Y each independently consists of an aromatic group, an alicyclic group, an aliphatic group, a siloxane group, and a group having a complex structure thereof. It is preferable that it is group chosen from.

In said formula (1)-(3), X is a following structure:

[Formula 9]

It is more preferable that it is an aromatic group chosen from the group which consists of groups represented by, and it is more preferable that it is an aromatic group which removed the carboxyl group and the amino group in the amino-substituted isophthalic acid structure.

In formulas (1) to (3), Y is more preferably a cyclic organic group having 1 to 4 aromatic rings or aliphatic rings which may be substituted, or an aliphatic group or siloxane group not having a cyclic structure. Specifically, preferred examples of the cyclic organic group include the following aromatic groups or alicyclic groups:

[Formula 10]

[Formula 11]

(In formula, A is 1 group each independently chosen from the group which consists of a hydroxyl group, a methyl group, an ethyl group, a propyl group, and a butyl group, and also contains various isomers in a propyl group and a butyl group.)

[Formula 12]

{In formula, p and q are each independently the integer of 0-3, r is the integer of 0-8, s and t are the integers of 0-10 each independently, B is a methyl group, an ethyl group, a propyl group, Butyl group or isomers thereof}. In the above formula, p and q each represent the number of repetitions of the methylene chain, r, s and t each represent the number of substitution on the ring of substituent B, and B represents a substituent on the ring, especially a hydrocarbon group having 1 to 4 carbon atoms. .

Moreover, the preferable example of the aliphatic group or siloxane group which does not have a cyclic structure is the following:

[Formula 13]

{In formula, a is an integer of 2-12, b is an integer of 1-3, c is an integer of 1-20, R <_3> and R <_4> is a C1-C3 alkyl group each independently, or is substituted. It may be a phenyl group which may be}}.

It is preferable that W in Formula (2) and (3) is an aromatic group, an aliphatic group, or an alicyclic group, respectively. Preferred aromatic groups include the following groups:

[Formula 14]

The polyamide resin of this invention can be synthesize | combined as follows, for example.

Synthesis of Phthalic Acid Compound Bag

Firstly, a compound having a trivalent aromatic group X (group corresponding to X in the above-described formulas), for example, a group consisting of phthalic acid substituted with an amino group, isophthalic acid substituted with an amino group, and terephthalic acid substituted with an amino group 1 mol or more of compounds selected from the following (hereinafter referred to as a "phthalic acid compound") and 1 mol of one or more compounds reacting with an amino group are reacted to contain a radically polymerizable unsaturated bond described later. The compound (Hereinafter, it is called a "phthalic-acid compound sealing body") is synthesize | combined by the 1 or more types of group which were sealed.

The structure which sealed the phthalic acid compound with the group containing the said radically polymerizable unsaturated bond can give negative photosensitive property (namely, photocurability) to a polyamide resin. It is preferable that the group containing a radically polymerizable unsaturated bond is a C5-C20 aliphatic group which has a radically polymerizable unsaturated bond group from a photosensitive characteristic and chemical-resistance viewpoint, and is a methacryloyloxymethyl group and / or acryloyloxy Particular preference is given to aliphatic groups containing methyl groups.

The phthalic acid compound sealing body mentioned above can be obtained by making the C5-20 aliphatic acid chloride, aliphatic isocyanate, or aliphatic epoxy compound etc. which have at least one amino group of a phthalic acid compound, and a radically polymerizable unsaturated bonding group react. Preferred aliphatic acid chlorides include 2-[(meth) acryloyloxy] acetyl chloride, 3-[(meth) acryloyloxy] propionyl chloride, 2-[(meth) acryloyloxy] ethylchloroform Mate, 3-[(meth) acryloyloxypropyl] chloroformate, and the like. Preferred aliphatic isocyanates include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxymethyl] ethyl isocyanate and 2- [2- (meth) acryloyloxyethoxy ] Ethyl isocyanate] etc. are mentioned. As a preferable aliphatic epoxy compound, glycidyl (meth) acrylate etc. are mentioned. These may be used independently, and may mix and use 2 or more types. Particular preference is given to using 2-methacryloyloxyethyl isocyanate.

As the phthalic acid compound encapsulating body, it is preferable that the phthalic acid compound is 5-aminoisophthalic acid because it is excellent in photosensitive characteristics and a polyamide resin having excellent film properties after heat curing can be obtained.

The said sealing reaction can be advanced by stirring, dissolving, and mixing a phthalic acid compound and an sealing agent in a reaction solvent in presence of basic catalysts, such as a pyridine, or tin type catalysts, such as di-n-butyltin dilaurate.

As the reaction solvent, it is preferable to completely dissolve the phthalic acid compound encapsulation product, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl Sulfoxide, tetramethylurea, gamma -butyrolactone, and the like.

In addition, as a reaction solvent, ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons are mentioned, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetic acid Methyl, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichloro Benzene, hexane, heptane, benzene, toluene, xylene and the like. These solvents may be used alone or in combination of two or more kinds as necessary.

Depending on the kind of sealing agent, such as an acid chloride, hydrogen chloride may by-produce in the process of sealing reaction. In this case, even in the sense of preventing contamination of the subsequent steps, the product is properly purified, for example, by reprecipitating the product with water, drying with water, or passing through a column filled with an ion exchange resin to remove and reduce ionic components. It is preferable.

Synthesis of Polyamide Resin

Secondly, the diamine compound which has the said phthalic-acid compound sealing body and divalent or tetravalent organic group Y (group corresponding to Y in each above-mentioned formula) is suitable in presence of basic catalysts, such as a pyridine and a triethylamine, The polyamide resin of this invention can be obtained by mixing in a solvent and carrying out amide polycondensation.

As desired, a part of the phthalic acid compound encapsulating body may be used in combination with a dicarboxylic acid having a divalent organic group W (a group corresponding to W in each formula described above). About a combination ratio, it is preferable to make the ratio in the total number of all the structural units of a polyamide resin of the number of the structure derived from a phthalic acid compound sealing body into 80% or more and 100% or less. If it is the said combined ratio, the photosensitive characteristic at the time of ultraviolet exposure, and the film | membrane characteristic after heat hardening, especially chemical resistance can be improved to the level which this invention expects.

As said amide polycondensation method, after dicarboxylic acid component (dicarboxylic acid which has a phthalic acid compound encapsulation body and divalent organic group W; below) is made into symmetric polyacid anhydride using a dehydration condensing agent, it is diamine. A method of mixing with a compound, a method of mixing the dicarboxylic acid component with a diamine compound after acid chloride by a known method, and reacting the dicarboxylic acid component with an active esterifying agent in the presence of a dehydrating condensing agent to activate the ester. After the compounding, a method of mixing the product with the diamine compound and the like can be given.

Preferred dehydrating condensing agents include, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1'-carbonyldioxy-di-1 , 2,3-benzotriazole, N, N'-disuccinimidyl carbonate and the like.

Examples of the chloroating agent include thionyl chloride and the like.

As the active esterification agent, N-hydroxysuccinimide, 1-hydroxybenzotriazole, N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide, 2-hydroxyimino-2 Ethyl cyanoacetate, 2-hydroxyimino-2-cyanoacetic acid amide, and the like.

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, and 3,3. '-Diphenyletherdicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 3,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4' -Benzophenonedicarboxylic acid, 3,4'-benzophenonedicarboxylic acid, 3,3'-benzophenonedicarboxylic acid, 4,4'-hexafluoroisopropylidene2benzoic acid, 4,4 ' -Dicarboxydiphenylamide, 1,4-phenylenediethanic acid, 1,1-bis (4-carboxyphenyl) -1-phenyl-2,2,2-trifluoroethane, bis (4-carboxyphenyl) Sulfide, bis (4-carboxyphenyl) tetraphenyldisiloxane, bis (4-carboxyphenyl) tetramethyldisiloxane, bis (4-carboxyphenyl) sulfone, bis (4-carboxyphenyl) methane, 5-tert-butyl Isophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 4-hydric Isophthalic 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-phenylenedioxy) 2benzoic acid, 2,6-naphthalenedicarboxylic acid In addition to aromatic dicarboxylic acids such as succinic acid, adipic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, malic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicar Aliphatic dicarboxylic acid and alicyclic dicarboxylic acid, such as an acid and 5-norbornene-2,3-dicarboxylic acid, are mentioned.

As the diamine compound having an organic group Y, at least one diamine compound 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 is preferable. You may use together multiple types as desired.

As an aromatic diamine compound, p-phenylenediamine, m-phenylenediamine, 4,4'- diamino diphenyl ether, 3,4'- diamino diphenyl ether, 3,3'- diamino diphenyl ether , 4,4'-diaminodiphenylsulfide, 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'-diaminodiphenyl Methane, 3,3'-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-amino Phenoxy) 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-amino Phenyl) 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 a part of the hydrogen atoms on these benzene rings is a group consisting of methyl group, ethyl group, hydroxymethyl group, hydroxyethyl group, and halogen atom The diamine compound substituted by the 1 or more group chosen from is mentioned.

Examples of the diamine compound 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'-diamino ratio Phenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, etc. are mentioned.

-메틸벤질리덴)-비스(2-아미노페놀) 등을 들 수 있다. As an aromatic bisaminophenol compound, 3,3'- dihydroxybenzidine, 3,3'- diamino-4,4'- dihydroxy biphenyl, 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 '-Diaminodiphenylether, 4,4'-dihydroxy-3,3'-diaminodiphenylether, 2,5-dihydroxy-1,4-diaminobenzene, 4,6-diamino Resorcinol, 1,1-bis (3-amino-4-hydroxyphenyl) cyclohexane, 4,4- (

-Methylbenzylidene) -bis (2-aminophenol), etc. are mentioned.

As an alicyclic diamine compound, 1, 3- diamino cyclopentane, 1, 3- diamino cyclohexane, 1, 3- diamino- 1-methyl cyclohexane, 3, 5- diamino- 1, 1- dimethyl Cyclohexane, 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, norbornanediamine, 1-cyclohepten-3,7-diamine, 4,4'-methylenebis (cyclohexylamine), 4 , 4'-methylenebis (2-methylcyclohexylamine), 1,4-bis (3-aminopropyl) piperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetra Oxaspiro- [5,5] -undecane etc. are mentioned.

As a linear aliphatic diamine compound, 1, 2- diamino ethane, 1, 4- diamino butane, 1, 6- diamino hexane, 1, 8- diamino octane, 1, 10- diamino decane, 1, Hydrocarbon type diamines, such as 12-diaminododecane, 2- (2-aminoethoxy) ethylamine, 2,2 '-(ethylenedioxy) diethylamine, bis [2- (2-aminoethoxy) ethyl ] Alkylene oxide type diamines, such as ether, etc. are mentioned.

Dimethyl (poly) siloxane diamine, for example, Shin-Etsu Chemical Co., Ltd. brand name PAM-E, KF-8010, X-22-161A etc. are mentioned as a siloxane diamine compound.

As a reaction solvent, the solvent which melt | dissolves the produced polymer completely is preferable, For example, N-methyl- 2-pyrrolidone, N, N- dimethylacetamide, N, N- dimethylformamide, dimethyl sulfoxide , Tetramethylurea, γ-butyrolactone, and the like.

In addition, in some cases, ketones, esters, lactones, ethers, hydrocarbons and halogenated hydrocarbons may be used as the 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-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene and the like.

After completion | finish of an amide polycondensation reaction, the precipitate etc. derived from the dehydration condensation agent which precipitated in the reaction liquid are isolate | separated as needed. Subsequently, a poor solvent of polyamide such as water or aliphatic lower alcohol or a mixture thereof is added to the reaction solution to precipitate the polyamide. In addition, the precipitated polyamide is redissolved in a solvent, purified by repeating the reprecipitation precipitation operation, and vacuum dried to isolate the desired polyamide. In addition, in order to further improve the degree of purification, the polyamide solution may be passed through a column filled with an ion exchange resin to remove ionic impurities.

It is preferable that it is 7,000-70,000, and, as for the polystyrene conversion weight average molecular weight by the gel permeation chromatography (henceforth "GPC") of the polyamide resin of this invention, it is more preferable that it is 10,000-50,000. When the polystyrene reduced weight average molecular weight is 7,000 or more, the basic physical properties of the cured relief pattern are good. Moreover, when the polystyrene reduced weight average molecular weight is 70,000 or less, the development solubility at the time of forming a relief pattern is favorable.

As the eluent of GPC, tetrahydrofuran and N-methyl-2-pyrrolidone are recommended. In addition, a weight average molecular weight value is calculated | required from the analytical curve created using standard monodisperse polystyrene. As standard monodisperse polystyrene, it is recommended to select from Showa Denko organic solvent-based standard sample STANDARD SM-105.

<Photosensitive resin composition>

This invention also provides the photosensitive resin composition containing (A) 100 mass parts of polyamide resins (henceforth (A) polyamide resin) of this invention, and (B) 0.5-20 mass parts of photoinitiators. . The specific aspect of the (A) polyamide resin which can be used for the photosensitive resin composition of this invention is as above-mentioned. In the photosensitive resin composition of this invention, it is used combining the said (A) polyamide resin and (B) photoinitiator from a viewpoint of providing photosensitive characteristic.

(B) photoinitiator

(B) As a photoinitiator, the compound known conventionally can be used as a photoinitiator of polyamide. Preferred examples include, for example,

[1] benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone and fluorenone

[2] 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl Phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2 Acetophenone derivatives such as -methyl propionyl) -benzyl] -phenyl} -2-methylpropane-1-one and methyl phenylglyoxylate

[3] thioxanthone derivatives such as thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone and diethyl thioxanthone

[4] benzyl derivatives such as benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal

[5] benzoin derivatives such as benzoin, benzoin methyl ether and 2-hydroxy-2-methyl-1-phenylpropan-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-diphenylpropanetri On-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 Oxime compounds such as

-히드록시케톤계 화합물 [7] 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane- 1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropane, etc.

Hydroxyketone compounds

-아미노알킬페논계 화합물 [8] 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholine- Such as 4-yl-phenyl) butan-1-one

-Aminoalkylphenone compounds

[9] bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6- Phosphine oxide compounds such as trimethylbenzoyl-diphenyl-phosphine oxide

[10] titanocene compounds such as bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium Etc. can be mentioned. In addition, these photoinitiators may be used individually as desired and may be used in mixture of 2 or more types.

In said photoinitiator, the oxime of [6] is more preferable especially from a viewpoint of photosensitivity. It is preferable that it is 0.5-20 mass parts, and, as for the compounding quantity of (B) photoinitiator with respect to 100 mass parts of (A) polyamide resin, it is more preferable that it is 1-10 mass parts. When the said compounding quantity is 0.5 mass part or more, at the time of exposure, radical enough to fully advance radical photopolymerization is supplied, and sufficient photosensitivity is ensured practically, and the 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, the exposure light ray can be reached to the vicinity of a board | substrate surface favorable, and it can advance uniform optical radical polymerization in a film thickness direction. And a relief pattern suitable for practical use can be obtained.

(C) monomers having a photopolymerizable unsaturated bond

The photosensitive resin composition of this invention can further contain the monomer which has (C) photopolymerizable unsaturated bond, in order to improve the photosensitive characteristics, such as a sensitivity and a resolution. As (C) monomer which has a photopolymerizable unsaturated bond, the (meth) acryl compound which can be radically polymerized by the above-mentioned (B) photoinitiator is preferable, For example, polyethyleneglycol diacrylate (the number of each ethylene glycol unit) 2 to 20), polyethylene glycol dimethacrylate (number of each ethylene glycol unit 2 to 20), poly (1,2-propylene glycol) diacrylate, poly (1,2-propylene glycol) dimethacrylate, Pentaerythritol diacrylate, pentaerythritol dimethacrylate, glycerol diacrylate, glycerol dimethacrylate, dipentaerythritol hexaacrylate, methylenebisacrylamide, N-methylol acrylamide, ethylene glycol diglycol Cedyl ether methacrylic acid adduct, glycerol diglycidyl ether acrylic acid adduct, bisphenol A diglycidyl ether acrylic acid adduct, bisphenol A diglycid Ether methacrylic acid addition and the like can be water, N, N'- bis (2-methacryloyloxyethyl) urea. These may be used individually as needed, or may mix and use 2 or more types.

(A) It is preferable that it is 1-40 mass parts, and, as for the compounding quantity of the monomer which has (C) photopolymerizable unsaturated bond with respect to 100 mass parts of polyamide resins, it is more preferable that it is 1-20 mass parts. When the said compounding quantity is 1 mass part or more, at the time of exposure, the optical crosslinking (photoradical polymerization) in an exposure part fully advances, sufficient photosensitivity sufficient for practical use is ensured, and the relief pattern suitable for practical use can be obtained. Moreover, when the said compounding quantity is 40 mass parts or less, unnecessary photocuring in the unexposed part by the leakage of the light from an exposure part, ie, residue after image development, can be suppressed and the relief pattern suitable for practical use can be obtained. Moreover, since the residual monomer component used as the degassing component from a cured film can also be suppressed at the time of low temperature hardening, it is preferable.

(D) thermocrosslinkable compound

The photosensitive resin composition of this invention can further contain the (D) heat crosslinkable compound in order to improve the film | membrane characteristic (especially heat resistance) after heat-hardening. (D) A thermal crosslinkable compound is a compound which (A) heat-crosslinks a polyamide resin, or is a compound which itself forms a thermal crosslinking network. As the heat crosslinkable compound (D), a compound having an alkoxymethyl group as the heat crosslinkable group, for example, an amino resin or a derivative thereof, is preferably used. Among them, urea resins, glycol urea resins, hydroxyethylene urea resins, melamine resins, benzoguanamine resins, and derivatives thereof are preferably used. Especially preferably, it is hexamethoxymethylated melamine.

It is preferable that it is 1-20 mass parts, and, as for the compounding quantity of (D) heat crosslinkable compound with respect to 100 mass parts of (A) polyamide resin, it is more preferable that it is 3-15 mass parts. When the said compounding quantity is 1 mass part or more, the film | membrane characteristic after heat-hardening of the photosensitive resin composition of this invention can be improved further. Moreover, when the said compounding quantity is 20 mass parts or less, even in low temperature hardening, the residual monomer component used as the degassing component from a cured film can be suppressed.

(E) Silane Coupling Agent

It is preferable that the photosensitive resin composition of this invention contains the (E) silane coupling agent in order to improve the photosensitive characteristics, such as adhesiveness at the time of image development. As the (E) 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:

[Formula 15]

{Wherein 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, and G is a carbon directly bonded to a silicon atom A divalent organic group containing an atom, d is an integer of 0 or 1, R ₅ is a hydrogen atom or a monovalent hydrocarbon group, R ₆ and R ₇ are each independently an alkyl group having 1 to 4 carbon atoms, and e Is an integer of 0 or 1}.

The silane coupling agent can be obtained by reacting a (dialkoxy) monoalkylsilyl compound or a (trialkoxy) silyl compound having an amino group with dicarboxylic anhydride or tetracarboxylic dianhydride and derivatives thereof.

As dicarboxylic acid anhydride or tetracarboxylic dianhydride, and its derivative (s), various structures can be used, for example, maleic anhydride, phthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride , 4-methylcyclohexane-1,2-dicarboxylic acid anhydride, 1-cyclo hexene-1,2-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 1, 2-naphthalic anhydride, 1,8-naphthalic anhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-di Phenylsulfontetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoroisopropylidenetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylethertetra Carboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'- Diphenyl tetracarboxylic dianhydride etc. are mentioned.

Among them, phthalic anhydride and 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride are particularly preferred in view of the effect of good 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, for example, the following may be mentioned (hereinafter, alkoxy denotes a methoxy group or Refers to an ethoxy group):

2-aminoethyltrialkoxysilane, 3-aminopropyltrialkoxysilane, 3-aminopropyldialkoxymethylsilane, 2-aminoethylaminomethyltrialkoxysilane, 2-aminoethylaminomethyldiakoxymethylsilane, 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 consideration of the effect and price of adhesion to the underlying substrate, 3-aminopropyltriethoxysilane is particularly preferred.

In addition, you may use as what was illustrated as the (dialkoxy) monoalkylsilyl compound and (trialkoxy) silyl compound which have the said amino group as a silane coupling agent as it is.

Further, N-trialkoxysilyl-1,2,4-triazole, N-trialkoxysilylimidazole, N-trialkoxysilylpyrrole, N-trialkoxysilylpyridine, N-trialkoxysilylpyrrolidine, py Periinomethyltrialkoxysilane, 2-piperidinoethyltrialkoxysilane, 3-morpholinopropyltrialkoxysilane, 3-piperazinopropyltrialkoxysilane, 3-piperidinopropyltrialkoxysilane, 3- ( 4-methylpiperazinopropyl) trialkoxysilane, 3- (4-methylpiperazinopropyl) trialkoxysilane, 4- (2-trialkoxysilylethyl) pyridine, N- (3-trialkoxysilylpropyl)- Heterocyclic containing organosilicon compounds, such as 4, 5- dihydroimidazole, 2- (2-trialkoxy silyl ethyl) pyridine, and N- (3-trialkoxy silyl propyl) pyrrole, are mentioned.

In addition, vinyltrialkoxysilane, 1-propenyltrialkoxysilane, 2-propenyltrialkoxysilane, 3-methacryloyloxypropyltrialkoxysilane, 3-acryloyloxypropyltrialkoxysilane, 3-methacryl Oxypropylmethyl dialkoxysilane, 3-acryloxypropylmethyl dialkoxysilane, p-styryltrialkoxysilane, p- (1-propenylphenyl) trialkoxysilane, p- (2-propenylphenyl) trialkoxysilane And organosilicon compounds containing carbon-carbon unsaturated bonds.

In addition, 2- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropylmethyl dialkoxysilane, p-styryltrialkoxysilane, N-2 -(Aminoethyl) -3-aminopropyltrialkoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiakoxysilane, 3-trialkoxysilyl-N- (1,3-dimethyl-butylidene ) Propylamine, N-phenyl-3-aminopropyltrialkoxysilane, 3-ureidopropyltrialkoxysilane, 3-ureidopropylmethyl dialkoxysilane, 3-mercaptopropyltrialkoxysilane, 3-mercaptopropylmethyl Dialkoxysilane, bis (trialkoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltrialkoxysilane, 6-trialkoxysilyl-2-norbornene, dialkoxydodecylmethylsilane, 3- (trialkoxysilyl ) Propyl succinic anhydride, N- (3-dialkoxymethylsilylpropyl) succinimide, N- [3- (trialkoxysilyl) propyl] phthala Deusan, the N- [3- (trialkoxy silyl) propyl] phthalimide, N- [3- (dialkoxy silyl) propyl] phthalimide may include imide and the like.

(E) A silane coupling agent may be independent or a mixture of 2 or more types may be sufficient as it. It is preferable that it is 0.1-25 mass parts, and, as for the compounding quantity of (E) silane coupling agent with respect to 100 mass parts of (A) polyamide resin, it is more preferable that it is 0.3-20 mass parts. When the said compounding quantity is 0.1 mass part or more, the effect of improving the adhesiveness of the photosensitive resin with respect to a base substrate is favorable. Moreover, when the said compounding quantity is 25 mass parts or less, the fear of precipitation by the dark reaction of the silane coupling agents in the photosensitive resin composition is drastically reduced.

(F) Benzotriazole Compound

It is preferable that the photosensitive resin composition of this invention contains (F) benzotriazole type compound in order to improve the adhesiveness of the photosensitive resin on a board | substrate (especially a copper substrate), or to suppress discoloration of the copper substrate. . Examples of the (F) benzotriazole-based compound 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 (hydr Hydroxyethyl) aminomethyl] -4 (or 5) -methylbenzotriazole, 1-hydroxymethylbenzotriazole, 1-[(2-ethylhexylamino) methyl] -benzotriazole, 1- (1 ', 2'-dicarboxyethyl) benzotriazole, N-benzotriazolemethylurea, 2,6-bis [(1H-benzotriazol-1-yl) methyl] 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, etc. are mentioned.

Especially, 4 (or 5) -carboxybenzotriazole and 4 (or 5) -methylbenzotriazole are especially preferable.

(F) A benzotriazole type compound may be independent or a mixture of 2 or more types may be sufficient as it. It is preferable that it is 0.1-10 mass parts, and, as for the compounding quantity of (F) benzotriazole type compound with respect to 100 mass parts of (A) polyamide resin, it is more preferable that it is 0.5-5 mass parts. When the said compounding quantity is 0.1 mass part or more, the adhesiveness of the photosensitive resin on a board | substrate (especially a 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 a copper substrate) can be suppressed.

Other Ingredients: Sensitizer

The photosensitive resin composition can also be made to contain a sensitizer for improving photosensitivity as desired. As such a sensitizer, For example, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2, 5-bis (4'- diethylamino benzylidene) cyclopentanone, 2, 6 -Bis (4'-diethylaminobenzylidene) cyclohexanone, 2,6-bis (4'-dimethylaminobenzylidene) -4-methylcyclohexanone, 2,6-bis (4'-diethylamino Benzylidene) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, 2- (4'-dimethylaminocinnamylidene) indanon , 2- (4'-dimethylaminobenzylidene) indanon, 2- (p-4'-dimethylaminobiphenyl) benzothiazole, 1,3-bis (4-dimethylaminobenzylidene) acetone, 1,3 -Bis (4-diethylaminobenzylidene) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7- Dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-e Cycarbonyl-7-diethylaminocoumarin, N-phenyl-N-ethylethanolamine, N-phenyldiethanolamine, Np-tolyl diethanolamine, N-phenylethanolamine, N, N-bis (2-hydride Oxyethyl) aniline, 4-morpholinobenzophenone, 4-dimethylaminobenzoic acid isoamyl, 4-diethylaminobenzoic acid isoamyl, 1,2,3-benzotriazole, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-1,2,3,4-tetazole, 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-dimethylaminostyryl) benzothiazole , 2- (p-dimethylaminostyryl) naphtho (1,2-p) thiazole, 2- (p-dimethylaminobenzoyl) styrene, and the like.

The sensitizer to be used may be single or a mixture of 2 or more types. It is preferable that it is 0-15 mass parts with respect to 100 mass parts of (A) polyamide resin, and, as for the compounding quantity of a sensitizer, it is more preferable that it is 1-10 mass parts.

Other components: polymerization inhibitor

As needed, the photosensitive resin composition of this invention can also contain a polymerization inhibitor for the purpose of the improvement of the viscosity of the photosensitive resin composition solution at the time of storage, and stability of photosensitivity. As such a polymerization inhibitor, for example, hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexane Diamine tetraacetic acid, glycol ether diamine tetraacetic 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-phenylhydroxyamineammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N- (1-naphthyl) hydroxyamineammonium salt, bis (4-hydroxy-3,5-di-tert-butyl) phenylmethane and the like can be used.

It is preferable that it is 0-5 mass parts with respect to 100 mass parts of (A) polyamide resin, and, as for the compounding quantity of a polymerization inhibitor, it is more preferable that it is 0.01-1 mass part. When the said compounding quantity is 5 mass parts or less, the photosensitivity suitable for practical use can be ensured favorably, without inhibiting the expected photocrosslinking reaction.

Unless the effect of this invention is impaired, the photosensitive resin composition of this invention can mix | blend various additives, such as a scattered light absorbing agent and a coating film smoothening agent, as needed in addition to the above.

<Photosensitive resin composition solution>

-아세틸-γ-부티로락톤, 테트라메틸우레아, 1,3-디메틸-2-이미다졸리논, N-시클로헥실-2-피롤리돈 등을 들 수 있고, 이들은 단독 또는 2 종 이상의 조합으로 사용할 수 있다. 이들 중에서도, N-메틸-2-피롤리돈 및γ-부티로락톤이 특히 바람직하다. This invention also provides the photosensitive resin composition of this invention mentioned above, and the photosensitive resin composition solution which consists of a solvent. It is preferable to use the photosensitive resin composition solution whose viscosity was adjusted by adding a solvent to the photosensitive resin composition. Preferred solvents include N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide and hexamethylphosphoramide , Pyridine, cyclopentanone, γ-butyrolactone,

-Acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, and the like, and these may be used alone or in combination of two or more thereof. Can be used. Among these, N-methyl-2-pyrrolidone and (gamma) -butyrolactone are especially preferable.

Although these solvent can be suitably added to the photosensitive resin composition of this invention according to the coating film thickness and viscosity of the photosensitive resin composition solution, it uses in 100-1,000 mass parts with respect to 100 mass parts of (A) polyamide resins. It is desirable to.

In order to improve the storage stability, etc. of the photosensitive resin composition, in addition to the above-mentioned thing, alcohol shown below can also be used together. The alcohols are not particularly limited as long as they have an alcoholic hydroxyl group in the molecule. Specific examples thereof 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) Mono alcohols such as ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono (n-propyl) ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monophenyl ether, ethylene glycol And dialcohols, such as propylene glycol, are mentioned. Among these, benzyl alcohol and ethylene glycol monophenyl ether are particularly preferable.

When using these alcohol together, it is preferable that the content rate which occupies for the whole solvent is 50 mass% or less. When the said ratio exceeds 50 mass%, there exists a tendency for the solubility to the solvent of (A) polyamide resin to fall.

<Formation method of the hardening relief pattern>

This invention applies the photosensitive resin composition of this invention or the photosensitive resin composition solution of this invention mentioned above on a base material, and forms the coating film of the photosensitive resin composition, and an actinic light through the coating film directly or through a patterning mask. Formation of a cured relief pattern comprising an exposure step of irradiating light, a developing step of forming a relief pattern by dissolving and removing an unexposed part of the coating film using a developer, and a step of heating and curing the relief pattern to form a cured relief pattern. It also provides a method. An 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 this invention is apply | coated on base materials, such as a silicon wafer, an aluminum substrate, and a copper substrate. As a coating apparatus or a coating method, a spin coater, a die coater, a spray coater, immersion, printing, a blade coater, roll coating, etc. can be used. A coating film is dried by the prebaking at 80-120 degreeC, and the coating film of the photosensitive resin composition is film-made about the film thickness of 5-50 microns.

Next, the coating film is exposed to the coating film formed above by irradiating active light directly or through a desired patterning mask (photomask) using an exposure projection device such as a contact aligner, a mirror projection, a stepper or the like. . X-rays, electron beams, ultraviolet rays, visible rays and the like can be used as the active light rays, but in the present invention, it is preferable to use active light rays having a wavelength of 200 to 500 nm.

After exposure, for the purpose of improving the photosensitivity, a post-exposure bake or a bake before development by an arbitrary temperature and time combination (preferably at a temperature of 40 ° C to 120 ° C and a time of 10 seconds to 240 seconds) You may carry out.

-아세틸-γ-부티로락톤, 시클로펜타논, 시클로헥사논 등을, 그리고 빈용매로는, 톨루엔, 자일렌, 메탄올, 에탄올, 이소프로판올, 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노메틸에테르, 물 등을 각각 사용할 수 있다. Subsequently, the development which dissolves and removes the unexposed part of the coating film using a developing solution and forms a relief pattern is performed. The developing method can be selected from methods such as an immersion method, a paddle method and a rotary spray method. As a developing solution, the good solvent of polyamide can be used individually, or the good solvent and poor solvent of polyamide can be mixed suitably, and can be used. Examples of good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide and γ-butyrolactone ,

-Acetyl-γ-butyrolactone, cyclopentanone, cyclohexanone and the like, and poor solvents include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, water Etc. can be used respectively.

When using a good solvent and a poor solvent in mixture, the mixing ratio is adjusted according to the solubility of the polyamide resin to be used, the developing method to be used, and the like.

For example, when using aromatic bisaminophenol as all or a part of the diamine compound which has the divalent or tetravalent organic group Y used for the polyamide resin of this invention, aqueous alkali solution can be used as a developing solution. As aqueous alkali solution, aqueous solution of inorganic alkalis, such as sodium hydroxide, sodium carbonate, sodium silicate, ammonia, aqueous solution of organic amines, such as ethylamine, diethylamine, triethylamine, and triethanolamine, tetramethylammonium hydroxide, tetra The aqueous solution, such as quaternary ammonium salts, such as butylammonium hydroxide, and what added the appropriate amount of water-soluble organic solvents, such as methanol and ethanol, surfactant, etc. to these aqueous alkali solution as needed can be used.

After completion of the development, a relief pattern is obtained by washing with a rinse solution as necessary and removing the developer. As a rinse liquid, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. can be used individually or in mixture of 2 or more types, and can also use 2 or more types It can also be used in combination in stages.

Thus, the relief pattern of the obtained polyamide is converted into the hardening relief pattern which consists of polyamide excellent in heat resistance and chemical-resistance, for example by heating suitably at 150-350 degreeC, and advancing heat-hardening and a crosslinking reaction. Such heat-hardening treatment can be performed using a hotplate, an inner oven, the temperature rising oven which can set a temperature program, etc. As an atmosphere at the time of heat-hardening, air may be used and inert gas, such as nitrogen and argon, may be used.

<Semiconductor Device>

선 차폐막, 격벽, 댐 등으로서 사용하고, 그 밖의 공정은 주지의 반도체 장치의 제조 방법을 적용함으로써, 반도체 장치를 제조할 수 있다. 또, 상기한 본 발명의 감광성 수지 조성물을 경화시켜 이루어지는 수지로 이루어지는 도포막을 갖는 반도체 장치를 얻을 수도 있다. This invention also provides the semiconductor device which has a hardening relief pattern formed by the formation method of the hardening relief pattern of this invention mentioned above. A surface protective film, an interlayer insulating film of a semiconductor device made of a cured relief pattern prepared as described above on a substrate such as a silicon wafer,

It is used as a line shielding film, a partition, a dam, etc., and the other process can manufacture a semiconductor device by applying a well-known semiconductor device manufacturing method. Moreover, the semiconductor device which has a coating film which consists of resin which hardens the photosensitive resin composition of above-mentioned this invention can also be obtained.

Example

Hereinafter, an Example and a comparative example demonstrate this invention. In addition, the combination list of the polymer raw material of each following synthesis example is shown in following Table 1.

Synthesis Example 1

(Synthesis of Phthalic Acid Compound Encapsulation Body AIPA-MO)

Into a separable flask with a capacity of 5 L, 5-aminoisophthalic acid (hereinafter abbreviated as AIPA) 543.5 g (3.0 mol) and 1,700 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) were charged. The mixture was stirred and heated to 50 ° C in a water bath. A dilution of 512.0 g (3.3 mol) of 2-methacryloyloxyethyl isocyanate with 500 g of γ-butyrolactone (hereinafter referred to as GBL) was added dropwise to the dropwise dropwise thereto, followed by 2 hours at 50 ° C. Stir it about.

After completion of the reaction (loss of 5-aminoisophthalic acid) was confirmed by low molecular weight gel permeation chromatography (hereinafter referred to as low molecular weight GPC), the reaction solution was added to 15 L of ion-exchanged water, stirred and allowed to stand. (Iii) and then wait for crystallization precipitation of the reaction product, filter, wash with water, and dry under vacuum at 40 ° C. for 48 hours to obtain an amino group of 5-aminoisophthalic acid and an isocyanate group of 2-methacryloyloxyethyl isocyanate. The functioned AIPA-MO was obtained. The low molecular weight GPC purity of the obtained AIPA-MO was approximately 100%.

Synthesis Example 2

(Synthesis of Phthalic Acid Compound Encapsulation Body AIPA-BA)

AIPA 543.5 g (3.0 mol) and NMP 1700g were thrown into the 5 liter separable flask, the mixture was stirred, and it heated to 50 degreeC by the water bath. What diluted 789.46 g (3.3 mol) of 1, 1-bis (acryloyl oxymethyl) ethyl isocyanate with 500 g of GBL was dripped at this, and it was dripped at the dropwise addition, and it stirred at 50 degreeC for about 2 hours.

After confirming completion of the reaction (dissipation of AIPA) by low molecular weight GPC, the reaction solution was poured into 15 L of ion-exchanged water, stirred and allowed to stand, and the crystallized precipitate of the reaction product was waited to be separated by filtration and washed with water appropriately. By vacuum-drying at 48 degreeC for 48 hours, AIPA-BA which the amino group of AIPA and the isocyanate group of 1, 1-bis (acryloyloxymethyl) ethylisocyanate acted was obtained. The low molecular weight GPC purity of the obtained AIPA-BA was almost 100%.

Synthesis Example 3

(Synthesis of Phthalic Acid Compound Encapsulation Body AIPA-ME)

AIPA 543.5 g (3.0 mol) and NMP 1700g were thrown into the 5 liter separable flask, the mixture was stirred, and it heated to 50 degreeC by the water bath. What diluted 657.38 g (3.3 mol) of 2- (2-methacryloyloxyethoxy) ethyl isocyanate with 500 g of GBL was dripped at this dropwise, and it stirred at 50 degreeC for 2 hours as it was.

After confirming completion of the reaction (dissipation of AIPA) by low molecular weight GPC, the reaction solution was poured into 15 L of ion-exchanged water, stirred and allowed to stand, and the crystallized precipitate of the reaction product was waited to be separated by filtration and washed with water appropriately. By vacuum-drying at 48 degreeC for 48 hours, AIPA-ME which the amino group of AIPA and the isocyanate group of 2- (2-methacryloyloxyethoxy) ethylisocyanate acted. The low molecular weight GPC purity of the obtained AIPA-ME was almost 100%.

Synthesis Example 4

(Synthesis of Phthalic Acid Compound Encapsulation Body AIPA-NBI)

AIPA 543.5 g (3.0 mol) and NMP 1700g were thrown into the 5 liter separable flask, the mixture was stirred, and it heated to 50 degreeC by the water bath. What diluted 541.73 g (3.3 mol) of 5-norbornene-2,3- dicarboxylic anhydrides with 500 g of GBL was dripped at this by the dropwise addition dropwise, and it stirred at 50 degreeC for about 10 hours as it was.

After completion of the reaction (disappearance of AIPA) was confirmed by low molecular weight GPC, and further completion of norbornene imidization (disappearance of carboxyl group) by FT-IR spectral analysis, the reaction solution was 15 L of ion exchange. After adding to water, stirring and standing, waiting for crystallization precipitation of the reaction product, filtration and washing with water were appropriately performed, and then vacuum drying at 40 ° C. for 48 hours, the amino group of AIPA and 5-norbornene-2,3-dicarboxyl An acid anhydride group of the acid anhydride acted to obtain AIPA-NBI having a norborneneimide structure. The low molecular weight GPC purity of the obtained AIPA-NBI was approximately 100%.

Synthesis Example 5

(Synthesis of Phthalic Acid Compound Encapsulation Body AIPA-MA)

Into a 5 L separable flask, AIPA 543.5 g (3.0 mol) and NMP 1700 g were charged and mixed. What diluted 344.97 g (3.3 mol) of methacrylic acid chlorides with 500 g of GBL was dripped at this, and it was dripped at the dropwise addition, and it stirred at room temperature for 2 hours as it is.

After confirming completion of the reaction (dissipation of AIPA) by low molecular weight GPC, the reaction solution was poured into 15 L of ion-exchanged water, stirred and allowed to stand, and the crystallized precipitate of the reaction product was waited to be separated by filtration and washed with water appropriately. By vacuum-drying at 48 degreeC for 48 hours, AIPA-MA which the amino group of AIPA and the acid chloride group of methacrylic acid chloride acted was obtained. The low molecular weight GPC purity of the obtained AIPA-MA was approximately 100%.

Synthesis Example 6

(Synthesis of Silane Coupling Agent S-1)

32.2 g (0.1 mol) of 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride and 206 g of NMP were injected | thrown-in to the capacity 1 L round bottom flask, and stirring was started. The solution which diluted 44.2 g (0.2 mol) of 3-aminopropyl triethoxysilanes with NMP100g was dripped, keeping this solution cooled to 0 degreeC. After completion | finish of dripping, returning this to room temperature and stirring for 4 hours, the acid anhydride group of 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, and the amino group of 3-aminopropyl triethoxysilane react, and half acid. A 20 mass% NMP solution of silane coupling agent S-1 that was / halmidated was obtained.

Synthesis Example 7

(Synthesis of Silane Coupling Agent S-2)

Into a 1 L round bottom flask, 29.6 g (0.2 mol) of phthalic anhydride and 195 g of N-methyl-2-pyrrolidone were injected, and stirring was started. While the solution was cooled to 0 ° C. and maintained, a solution obtained by diluting 3-aminopropyltriethoxysilane with 44.2 g (0.2 mol) of NMP 100 g was added dropwise. After completion | finish of dripping, returning this to room temperature and stirring for 4 hours, 20 mass% of the silane coupling agent S-2 in which the acid anhydride of phthalic anhydride and the amino group of 3-aminopropyl triethoxysilane reacted, and half acid / half-amidated. An NMP solution was obtained.

Synthesis Example 8

(Synthesis of Polyamide PA-1)

Into a 2 L separable flask, 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 the mixture was cooled to 5 ° C in an ice bath. . N, N-dicyclohexylcarbodiimide (hereinafter, referred to as DCC) was dissolved by diluting 125.0 g (0.606 mol) in 125 g of GBL, and added dropwise over 20 minutes under ice cooling, followed by 4 , 4'-bis (4-aminophenoxy) biphenyl {hereinafter, referred to as BAPB} A solution of 103.16 g (0.28 mol) dissolved in 168 g of NMP was added dropwise over about 20 minutes, and lower than 5 ° C in an ice bath. The ice bath was then released for 3 hours while maintaining and stirred at room temperature for 5 hours.

Thereafter, dicyclohexyl urea derived from the dehydrating condensation agent (hereinafter referred to as DCU) precipitated in the polycondensation process was filtered off under pressure, and the filtrate (polymer solution) was stirred, while 840 g of water and 560 g of isopropanol were stirred. Was added dropwise, the precipitated polymer was separated and redissolved in 650 g of NMP. This redissolved solution was added dropwise under stirring of 5 L of ion-exchanged water, and the polymer was dispersed and precipitated, recovered and washed with water, and then polyamide PA-1 was obtained by vacuum drying at 40 ° C for 48 hours. Polystyrene conversion GPC weight average molecular weight (column: Shodex KD-806Mx2, NMP flow rate: 1.0 ml / min) which measured NMP as an eluent was 34,700.

Synthesis Example 9

(Synthesis of Polyamide PA-2)

In a separable flask having a capacity of 2 L, 80.71 g (0.24 mol) of AIPA-MO obtained in Synthesis Example 1, 19.64 g (0.06 mol) of AIPA-NBI obtained in Synthesis Example 4, 71.2 g (0.9 mol) of pyridine, 400 g of GBL was thrown in and mixed, and the same operation as the synthesis example 8 was performed, and polyamide PA-2 was obtained. The polystyrene reduced GPC weight average molecular weight measured in the same manner 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, and 400 g of GBL It was charged and mixed and cooled to 5 ° C in an ice bath. To this, a solution obtained by diluting and diluting DCC 125.0 g (0.606 mol) in 125 g of GBL was added dropwise over 20 minutes under ice cooling, followed by 121.1 g (0.28 of bis [4- (4-aminophenoxy) phenyl] sulfone. Mol) was dissolved in 168 g of NMP over about 20 minutes, and the ice bath was released 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 reduced GPC weight average molecular weight measured by the same method as the synthesis example 8 was 32,000.

Synthesis Example 11

(Synthesis of Polyamide PA-4)

The same operation as in Synthesis Example 8 was carried out except that "BAPB 103.16 g (0.28 mol)" in Synthesis Example 8 was replaced with "56.07 g (0.28 mol) of 4,4'-diaminodiphenyl ether". Polyamide PA-4 was obtained. The polystyrene reduced GPC weight average molecular weight measured in the same manner as in Synthesis example 8 was 30,300.

Synthesis Example 12

(Synthesis of Polyamide PA-5)

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)” The same operation was performed and polyamide PA-5 was obtained. The polystyrene reduced GPC weight average molecular weight measured in the same manner as in Synthesis example 8 was 23,600.

Synthesis Example 13

(Synthesis of Polyamide PA-6)

In a 2 L separable flask, 84.08 g (0.25 mol) of AIPA-MO obtained in Synthesis Example 1, 101.35 g (0.75 mol) of 1-hydroxybenzotriazole, 39.6 g (0.5 mol) of pyridine, 4 5.6 g (0.05 mol) of dimethylaminopyridine and 275 g of N, N-dimethylformamide were added and mixed, and it cooled to 5 degreeC by the ice bath. After diluting and diluting DCC 134.11 g (0.65 mol) in 134 g of N, N-dimethylformamide, the mixture was added dropwise over 20 minutes under ice cooling, followed by stirring for 5 hours while maintaining cooling in an ice bath. Continued. 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 less than 5 ° C in an ice bath. Keeping for 3 hours followed by releasing the ice bath and stirring at room temperature for 10 hours.

Thereafter, the DCU precipitated in the polycondensation process was separated by pressure filtration, and a mixed solution of 1,000 g of water and 4,000 g of isopropanol was added dropwise while stirring the filtrate (polymer solution), and the precipitated polymer was separated, and the polymer was precipitated in NMP800 g. Redissolved. This redissolved solution was added dropwise under stirring of 5 L of ion-exchanged water, and the polymer was dispersed and precipitated. After recovery and washing with water, polyamide PA-6 was obtained by vacuum drying at 40 ° C for 48 hours. The polystyrene reduced GPC weight average molecular weight measured in the same manner as in Synthesis example 8 was 32,600.

Synthesis Example 14

(Synthesis of Polyamide PA-7)

Into a 1 L 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 added and mixed, and the mixture was cooled to 5 ° C in an ice bath. . The thing which melt | dissolved and diluted DCC 83.4g (0.404mol) in NMP83g was dripped at this over 20 minutes under ice-cooling, and then 2, 2-bis- (3-amino- 4-hydroxyphenyl) What dissolve 68.1 g (0.19 mol) of hexafluoropropane in 204 g of NMP was added over about 20 minutes, and the ice bath was canceled for 3 hours, and then stirred at room temperature for 10 hours, keeping the temperature below 5 ° C in an ice bath.

Thereafter, the DCU precipitated in the polycondensation process was separated by pressure filtration, and a mixed solution of 760 g of water and 190 g of isopropanol was added dropwise while stirring the filtrate (polymer solution), and the precipitated polymer was separated to obtain 400 g of NMP. Redissolved in The redissolved solution was added dropwise while stirring with 3 L of ion-exchanged water, and the polymer was dispersed and precipitated, recovered and washed with water, and then polyamide PA-6 was obtained by vacuum drying at 40 ° C for 48 hours. The polystyrene reduced GPC weight average molecular weight measured in the same manner as in Synthesis example 8 was 12,600.

Synthesis Example 15

(Synthesis of Polyamide PA-8)

Into a separable flask having a capacity of 2 L, 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, and then the same as in Synthesis Example 8 The operation was performed to obtain polyamide PA-8. The polystyrene reduced GPC weight average molecular weight measured in the same manner as in Synthesis example 8 was 33,000.

Synthesis Example 16

(Synthesis of Polyamide PA-9)

"BAPB 103.16 g (0.28 mol)" in the synthesis example 8 is referred to as 28.04 g (0.14 mol) and 2,2'-dimethyl-4,4'-diamino ratio of 4,4'- diamino diphenyl ether. Phenyl 29.72 g (0.14 mol) "was carried out similarly to the synthesis example 8, and polyamide PA-9 was obtained. The polystyrene reduced GPC weight average molecular weight measured in the same manner as in Synthesis example 8 was 28,200.

Synthesis Example 17

(Synthesis of Polyamide PA-10)

The same as in Synthesis Example 8, except that "BAPB 103.16 g (0.28 mol)" in Synthesis Example 8 was replaced with "BAPB 92.85 g (0.252 mol) and 1,8-diaminooctane 4.04 g (0.028 mol)" The operation was performed to obtain polyamide PA-10. The polystyrene reduced GPC weight average molecular weight measured in the same manner as in Synthesis example 8 was 26,800.

Synthesis Example 18

(Synthesis of Polyamide PA-11)

Into a 2 L separable flask, 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 the mixture was cooled to 5 ° C in an ice bath. . The thing which melt | dissolved and diluted DCC 125.0g (0.606mol) in 125g of GBL was dripped over about 20 minutes under ice-cooling, and then 2, 2-bis [4- (4-amino phenoxy) phenyl] propane The thing which melt | dissolved 103.45g (0.252mol) in 168g of NMP was dripped over about 20 minutes, and it was made to release | release an ice bath for 3 hours, and stirring at room temperature for 5 hours, keeping below 5 degreeC in an ice bath. Then, what mixed 36.4 g and 40 g of diethylene glycol dimethyl ethers by Shin-Etsu Chemical Co., Ltd. brand name KF-8010 which is both terminal amino-group-modified polydimethylsiloxane was dripped, and also it 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 reduced GPC weight average molecular weight measured in the same manner as in Synthesis example 8 was 28,000.

Synthesis Example 19

(Synthesis of Polyamide PA-12)

74.77 g (0.3 mol) of AIPA-MA obtained in the synthesis example 5, 71.2 g (0.9 mol) and 400 g of GBL were mixed and mixed in the 2 L separable flask, and it cooled to 5 degreeC by the ice bath. . The thing which melt | dissolved and diluted DCC 125.0g (0.606mol) in 125g of GBL was dripped at about 20 minutes under ice-cooling, Then, 56.07g (0.28mol) of 4,4'- diamino diphenyl ether was carried out NMP The thing dissolved in 168g was dripped over about 20 minutes, and the ice bath was canceled | released for 3 hours, and it stirred at room temperature for 5 hours, keeping below 5 degreeC in the ice bath. Thereafter, the same operation as in Synthesis Example 8 was performed to obtain polyamide PA-12. The polystyrene reduced GPC weight average molecular weight measured in the same manner as in Synthesis example 8 was 29,500.

Synthesis Example 20

(Synthesis of Polyamide PA-13)

Into a 2 L separable flask, 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 mixed and then mixed. The same operation as in Synthesis Example 8 was performed to obtain polyamide PA-13. The polystyrene reduced GPC weight average molecular weight measured in the same manner as in Synthesis example 8 was 32,100.

Synthesis Example 21

(Synthesis of Polyamide PA-14)

In a 2 L separable flask, 60.53 g (0.18 mol) of AIPA-MO, 30.99 g (0.12 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 the same operation as in Synthesis Example 8 was carried out to obtain polyamide PA-14. The polystyrene reduced GPC weight average molecular weight measured in the same manner as in Synthesis example 8 was 30,900.

Synthesis Example 22

(Synthesis of Polyimide Precursor PI-1)

To a 5 L separable flask, 310.22 g (1.00 mol) of diphenyl ether-3,3 ', 4,4'-tetracarboxylic dianhydride and 270.69 g (2.08) of 2-hydroxyethyl methacrylate Mol) and pyridine, 158.2 g (2.00 mol), 1000 g of GBL were charged and mixed, and it stirred at normal temperature for 16 hours. A solution obtained by diluting and diluting 400.28 g (1.94 mol) of DCC in 400 g of GBL was added dropwise over 30 minutes under ice cooling, and then 185.97 g (0.93 mol) of 4,4'-diaminodiphenyl ether was added to GBL. What was dispersed in 650 g was added over about 60 minutes. The mixture was stirred for 3 hours in an ice-cooled state, after which the ice-cooled bath was released, and further stirred for 1 hour. After the DCU precipitated in the polycondensation process was separated by pressure filtration, the reaction solution was added dropwise to 40 L of ethanol, and the polymer precipitated was separated and washed, and vacuum-dried at 50 ° C for 24 hours to give polyimide precursor PI. -1 was obtained. The polystyrene reduced GPC weight average molecular weight measured on the same conditions as the synthesis example 8 was 29,000.

Example 1

To 100 parts by mass of polyamide PA-1 obtained in Synthesis Example 8, 190 parts by mass of NMP was added and the polyamide PA-1 was dissolved to prepare a crude solution, which was filtered through a filter made of PTFE having a pore diameter of 0.2 μm. And the resin solution V-1 was obtained.

[Example 2]

In the crude solution in Example 1, it was the same as that of Example 1 except having added 5 mass parts of 1, 3- diphenyl propane trione 2- (O-ethoxycarbonyl) oximes as a photoinitiator further. It filtered, and obtained resin composition solution V-2.

Example 3

In the crude solution in Example 2, it filtered like Example 1 except having added 8 mass parts of tetraethylene glycol dimethacrylate as a photopolymerizable monomer, and obtained resin composition solution V-3. .

Example 4

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

Example 5

In the crude solution in Example 4, 5 mass parts (1 mass part as pure parts of S-1) of the 20 mass% NMP solution of the silane coupling agent S-1 obtained by the synthesis example 6 further, 10 mass parts (2 mass parts as a pure part of S-2), and 5 mass parts of 3- (trialkoxy silyl) propyl succinic anhydride were added to the 20 mass% NMP solution of the silane coupling agent S-2 obtained by the synthesis example 7 Except having filtered like Example 1, the resin composition solution V-5 was obtained.

Example 6

Except having added 2 mass parts of 5-carboxybenzotriazoles further in the crude solution in Example 5, it filtered like Example 1 and obtained resin composition solution V-6.

Example 7

5 parts by mass of 1,3-diphenylpropanetrione-2- (O-ethoxycarbonyl) oxime and tetraethylene glycol dimethacrylate relative to 100 parts by mass of the polyamide PA-1 obtained in Synthesis Example 8. 8 parts by mass, 5 parts by mass of hexamethoxymethylated melamine, and 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 a pure component of S-1), a synthesis example 10 parts by mass of the 20% by mass NMP solution of the silane coupling agent S-2 obtained in 7, {2 parts by mass as the pure component of S-2}, 5 parts by mass of 3- (trialkoxysilyl) propylsuccinic anhydride and 5-carboxybenzo 2 parts by mass of triazole, 5 parts by mass of N, N-bis (2-hydroxyethyl) aniline and 0.05 parts by mass of N-nitrosodiphenylamine were dissolved and dissolved in 190 parts by mass of NMP, and the pore diameter was 0.2 μm. It filtered with the PTFE filter, and obtained the resin composition solution V-7.

Example 8

3-Glycidoxy is substituted with the polyamide PA-1 used in Example 7 by PA-2 obtained in Synthesis Example 9, and the 3- (trialkoxysilyl) propylsuccinic anhydride used in Example 7 in the same manner Resin composition solution V-8 was obtained like Example 7 except having substituted with the propyl (dimethoxy) methylsilane.

Example 9

3-Isocyanato is substituted with the polyamide PA-1 used in Example 7 with PA-3 obtained in Synthesis Example 10, and the 3- (trialkoxysilyl) propylsuccinic anhydride used in Example 7 in the same manner. Resin composition solution V-9 was obtained like Example 7 except having substituted with the propyl triethoxysilane.

[Examples 10 to 17]

Except having substituted polyamide PA-1 used in Example 7 by polyamide PA-4-PA-11 obtained by the synthesis examples 11-18, respectively, it carried out similarly to Example 7, and the resin composition solution V-10- V-17 was obtained.

[Comparative Examples 1-3]

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

[Comparative Example 4]

Resin composition was carried out similarly to Example 7, except the polyamide PA-1 used in Example 7 was substituted with the polyimide precursor PI-1 obtained in the synthesis example 22, and the usage-amount of the solvent NMP was 165 mass parts. The solution V'-4 was obtained.

Note: Numerical values in parentheses in the table indicate mol%. In addition, about the symbol which is not defined above, it is as follows.

ODPA: diphenyl ether-3,3 ', 4,4'-tetracarboxylic dianhydride

DEDC: diphenyl ether-4,4'-dicarbonyldichloride

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 Characteristics and Adhesion During Development

The resin composition solutions of Examples 2-17 and Comparative Examples 1-4 were apply | coated on a 6 inch silicon wafer using the spin coater (Tokyo Electron make, model name Clean Truck Mark 8), and it is 95 minutes at 95 degreeC for 4 minutes. It prebaked and the coating film of 10 micrometers of initial film thicknesses was obtained. This coating film was made to pass through the photomask for evaluation by the i-line stepper exposure machine (The Nikon make, model name NSR2005i8A), and it exposed by changing 50 mJ / cm <2> in steps of exposure amount in the range of 100-1100 mJ / cm <2>.

After 30 minutes from the exposure, the coating film other than Example 13 was subjected to rotational spray development with a time multiplied by 1.4 by the time until the unexposed portion was completely dissolved and lost using cyclopentanone as a developing solution. It was then spray rinsed with propylene glycol monomethyl ether acetate for 10 seconds to obtain a relief pattern composed of a resin film. In the coating film of Example 13, after 30 minutes from exposure, the unexposed part was completely dissolved and lost using a 2.38% aqueous solution of tetramethylammonium hydroxide (manufactured by AZ Electronics, product number AZ-300MIF) as a developing solution. The paddle phenomenon of time multiplied by 1.4 multiplied by 1.4 was carried out, and the rotary stream rinse was continued with ion-exchange water, and the relief pattern which consists of a resin film was obtained.

The obtained relief pattern was visually observed under an optical microscope, and the minimum exposure amount (sensitivity) from which a sharp pattern without swelling was obtained, the size (resolution) of the via hole (rectangular concave pattern part) at the time of irradiation with the lowest exposure amount, and adhesion with the underlying (Lifting of the pattern and peeling) were evaluated. The results are shown in Table 2 below.

Evaluation of Mechanical Properties

After apply | coating and prebaking the resin composition solution of Examples 1-17 and Comparative Examples 1-4 on the 6-inch silicon wafer which vacuum-deposited the aluminum thin film in the same manner as the evaluation of the photosensitive characteristic mentioned above, And heat curing treatment at 180 ° C. for 2 hours in a nitrogen atmosphere using a vertical cure (Kouyou Lindberg, model name VF-2000B) to prepare a resin film having a film thickness of 10 μm after curing. This resin film was cut to 3.0 mm width using a dicing saw (made by Disco, model name DAD-2H / 6T), immersed in 10% hydrochloric acid aqueous solution, peeled from the silicon wafer, and it was set as the rectangular film sample. After leaving this film sample in the atmosphere of 23 degreeC and 55% RH for 24 hours or more, the tension test by tensilone based on ASTMD-882-88 was performed, and the elongation of the film sample was evaluated. 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 produced for evaluation of the mechanical properties was measured to be an index of the heat resistance of the resin film. Measurement conditions are a sample length of 10 mm, a static 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

On the 6-inch silicon wafer of 625 micrometers +/- 25 micrometers in thickness which measured "a warpage amount" previously, the resin composition solutions of Examples 1-17 and Comparative Examples 1-4 are the same conditions as the evaluation of the photosensitive characteristic mentioned above. After coating and prebaking, the resin film having a film thickness of 10 μm was cured by heating at 180 ° C. for 2 hours under a nitrogen atmosphere using a vertical curing agent (Kouyou Lindberg, model name VF-2000B). The formed silicon wafer was produced. The residual stress of this wafer was measured using the residual stress measuring apparatus (the Tencol company make, model name FLX-2320). The results are shown in Table 2 below.

Evaluation of chemical resistance

6, in which the resin composition solutions of Examples 1 to 17 and Comparative Examples 1 to 4 were previously treated with 3-aminopropyltriethoxysilane by using a spin coater (Tokyo Electron Co., Ltd., model name Clean Truck Mark 8). It applied on the inch silicon wafer, prebaked at 95 degreeC for 4 minutes, and obtained the coating film of 10 micrometers of initial film thicknesses.

The coating film was passed through a photomask for evaluation by an i-line stepper exposure machine (Nikon, model name NSR2005i8A), and was exposed under the condition of a constant exposure amount. The setting of the exposure amount added 200 mJ / cm <2> to each minimum exposure amount (sensitivity) by which the sharp pattern without swelling was obtained in evaluation of the photosensitive characteristic mentioned above.

After 30 minutes from exposure, the coating film other than Example 1 and Example 13 was subjected to the rotational spray phenomenon of time multiplied by 1.4 by the time until the unexposed portion was completely dissolved and lost using cyclopentanone as a developing solution. It carried out, and then spray-rinsed for 10 second with propylene glycol monomethyl ether acetate, and obtained the relief pattern which consists of a resin film. In the coating film of Example 13, after 30 minutes from exposure, the unexposed part was completely dissolved and lost using a 2.38% aqueous solution of tetramethylammonium hydroxide (manufactured by AZ Electronics, product number AZ-300MIF) as a developing solution. The paddle phenomenon of time multiplied by 1.4 multiplied by 1.4 was performed, and then the rotary stream rinse was performed with ion-exchange water, and the relief pattern which consists of a resin film was obtained.

The coating film of Example 1 was not developed because the coating film did not have photosensitivity.

The resulting relief pattern film (undeveloped flat film in Example 1) was cured by heating at 180 ° C. for 2 hours under a nitrogen atmosphere using a vertical curer (Kouyou Lindberg, model name VF-2000B). A relief pattern film (cured flat film about Example 1) was produced.

These cured films were heated for 5 minutes by heating a resist stripper (manufactured by ATMI, product name ST-44, main component of 2- (2-aminoethoxy) ethanol, 1-cyclohexyl-2-pyrrolidone) at 85 ° C. It was immersed and left to cool, washed with running water for 1 minute and dried in the wind. Thereafter, the surface of the film was visually observed under an optical microscope, and there was no damage due to chemicals such as cracks or roughness, and the rate of change of the film thickness before and after chemical treatment (unit%. 100% was no change in film thickness. The above evaluated chemical resistance by swelling and less than 100% of membrane dissolution). The results are shown in Table 3 below.

Cure  Evaluation of subsequent copper discoloration

In the resin composition solutions of Examples 2 to 17 and Comparative Examples 1 to 4, titanium was vacuum-deposited on a 6 inch silicon wafer using a spin coater (Tokyo Electron Co., Ltd., model name Clean Truck Mark 8). It was apply | coated to the board | substrate which carried out the base process by 3-aminopropyl triethoxysilane to copper vapor deposition from the above, and prebaked at 95 degreeC for 4 minutes, and obtained the coating film of 10 micrometers of initial film thicknesses.

The coating film was passed through a photomask for evaluation by an i-line stepper exposure machine (Nikon, model name NSR2005i8A), and was exposed under the condition of a constant exposure amount. The setting of the exposure amount added 200 mJ / cm <2> to each minimum exposure amount (sensitivity) by which the sharp pattern without swelling was obtained in evaluation of the photosensitive characteristic mentioned above.

After 30 minutes from the exposure, the coating film other than Example 13 was subjected to rotational spray development with a time multiplied by 1.4 by the time until the unexposed portion was completely dissolved and lost using cyclopentanone as a developing solution. It was then spray rinsed with propylene glycol monomethyl ether acetate for 10 seconds to obtain a relief pattern composed of a resin film. In the coating film of Example 13, after 30 minutes from exposure, the unexposed part was completely dissolved and lost using a 2.38% aqueous solution of tetramethylammonium hydroxide (manufactured by AZ Electronics, product number AZ-300MIF) as a developing solution. The paddle phenomenon of time multiplied by 1.4 multiplied by 1.4 was carried out, and the rotary stream rinse was continued with ion-exchange water, and the relief pattern which consists of a resin film was obtained.

To the relief pattern on the obtained copper substrate, using a vertical cure (Kouyou Lindberg, model name VF-2000B), heat curing treatment (cure) at 180 ° C. for 2 hours under a nitrogen atmosphere to cure the relief on the copper substrate. The pattern was prepared. The copper substrate surface of the unexposed part was visually observed under an optical microscope, and the color change of the copper surface after curing was evaluated. The results are shown in Table 3 below.

In Examples 1-17, the outstanding chemical-resistance is achieved also at the time of 180 degreeC low temperature hardening. At the same time, high mechanical properties showing elongation of 50% or more, excellent heat resistance showing Tg of 200 ° C or higher, and low residual stress characteristics of 25 MPa or less are achieved, and polyamide resins having excellent low-temperature curing characteristics and photosensitive properties containing them A resin composition can be provided.

In Examples 3 to 17, excellent photosensitivity can be obtained, and in Examples 4 to 17, excellent heat resistance can be obtained, and in Examples 5 to 17, excellent adhesiveness at development can be obtained, and In Examples 6-17, discoloration of the copper surface after curing was able to be suppressed.

On the other hand, the comparative example 1 is a case where the polyamide resin which used as a raw material the thing which introduced the radically polymerizable unsaturated bond group by the methacrylamide structure in which the methacryl group was directly connected to the amino group of AIPA (AIPA-MA) was used, but the unsaturated bond group The photoresist property is greatly inferior to the examples due to the low degree of freedom, and at the same time, the chemical resistance is also inferior to the examples.

In Comparative Examples 2 and 3, when the copolymerization ratio of the radical polymerizable unsaturated bond group introduced into the amino group of AIPA (for example, AIPA-MO) is less than the suitable range of the present invention, the radical polymerizable unsaturated bond group is reduced. At the same time as the deterioration of the photosensitive characteristic due to the decrease of the AIPA-derived structure, the chemical resistance also greatly falls in the examples.

Comparative Example 4 is a case where the resin film made of the photosensitive polyimide precursor composition of the prior art is cured at a low temperature of 180 ° C., whether the imidization is incomplete or not, in terms of mechanical properties, heat resistance, residual stress, and chemical resistance. More drastically.

선 차폐막 등의 내열성 도포막, 및 이미지 센서, 마이크로 머신 또는 마이크로 엑추에이터를 탑재한 반도체 장치 등에 있어서의 내열성 도포막의 형성에 사용되는 감광성 수지 조성물로서 바람직하다. The photosensitive resin composition of this invention, and the polyamide resin used for this are the insulating material of an electronic component, the surface protective film of a semiconductor device, the interlayer insulation film,

It is suitable as a photosensitive resin composition used for formation of the heat resistant coating film, such as a line shielding film, and the heat resistant coating film in the semiconductor device etc. which mounted an image sensor, a micromachine, or a micro actuator.

Claims (16)

Formula (1) below:
[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, and a carbon number when m = 2 It is a tetravalent organic group which is 6-35, R <_1> is the aliphatic group which has at least one C5-C20 radically polymerizable unsaturated bond group which may contain atoms other than carbon}, and repeats The polyamide resin which contains so that the repeating number may be in the range of 80 to 100% of the total number of all the structural units which comprise a polyamide resin within the range of numbers 2-150. Formula (2) below:
(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, and a carbon number when m = 2 and 6-35 of the tetravalent organic group, W is a carbon atoms, and 6-15 divalent organic group, and k is an integer of 1 or more, at the same time (n + k) is an integer in the range of 5 ~ 150, R ₁ is other than carbon Repeating number n in said Formula (2) makes the structure shown by the structure represented by the}} which is a C5-C20 aliphatic group which has at least 1 radically polymerizable unsaturated bond group which may contain the atom of the whole. The polyamide resin contained so that it may be 80% or more of the total number of structural units. Formula (3) below:
(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, and a carbon number when m = 2 Is a tetravalent organic group having 6 to 35, W is a divalent organic group having 6 to 15 carbon atoms, l is 0 or an integer of 1 or more, and at the same time (n + l) is an integer of 2 to 150, R ₁ is Only the structure represented by the C5-C20 aliphatic group which has at least 1 radically polymerizable unsaturated bond group which may contain atoms other than carbon as a structural unit, and repeating number n in said Formula (3) is poly The polyamide resin in 80 to 100% of the total number of all the structural units which comprise an amide resin. The method according to any one of claims 1 to 3,
R ₁ is represented by the following formula (4):
[Chemical Formula 4]

Polyamide resin which is group represented by {In formula, R <_2> is a C4-C19 aliphatic group which has at least 1 radically polymerizable unsaturated bond group. The method according to any one of claims 1 to 3,
The polyamide resin in which said R <_1> is group which has at least 1 (meth) acryloyloxymethyl group. The method according to any one of claims 1 to 3,
The polyamide resin in which W, X, and Y are each independently selected from the group consisting of an aromatic group, an alicyclic group, an aliphatic group, a siloxane group and a group of a complex structure thereof. (A) 100 parts by mass of the polyamide resin according to any one of claims 1 to 6, and
(B) Photosensitive resin composition containing 0.5-20 mass parts of photoinitiators. The method of claim 7, wherein
(C) Photosensitive resin composition which further contains the monomer which has a photopolymerizable unsaturated bond group at 1-40 mass parts with respect to 100 mass parts of polyamide resins of said (A). The method according to claim 7 or 8,
(D) The thermally 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 of the above-mentioned (A), and the (D) thermally crosslinkable compound thermally crosslinks the polyamide resin of the above-mentioned (A). The photosensitive resin composition which is a compound or a compound which itself forms a thermal crosslinking network. The method of claim 9,
The photosensitive resin composition in which the said (D) heat crosslinkable compound has an alkoxy methyl group as a heat crosslinkable group. The method according to any one of claims 7 to 10,
(E) Photosensitive resin composition which further contains a silane coupling agent at 0.1-25 mass parts with respect to 100 mass parts of polyamide resins of said (A). The method of claim 11,
The photosensitive resin composition whose said (E) silane coupling agent is an organosilicon compound which has a (dialkoxy) monoalkyl silyl group or a (trialkoxy) silyl group. The method according to any one of claims 7 to 12,
(F) Photosensitive resin composition which further contains a benzotriazole type compound at 0.1-10 mass parts with respect to 100 mass parts of polyamide resins of said (A). The photosensitive resin composition solution which consists of a photosensitive resin composition and solvent of any one of Claims 7-13. The process of apply | coating the photosensitive resin composition of any one of Claims 7-13 or the photosensitive resin composition solution of Claim 14 on a base material, and forming the coating film of the photosensitive resin composition,
An exposure step of irradiating actinic light directly on the coating film or via a patterning mask;
A developing step of forming a relief pattern by dissolving and removing unexposed portions of the coating film using a developing solution, and
A method of forming a cured relief pattern comprising a step of heating and curing the relief pattern to form a cured relief pattern. The semiconductor device which has a hardening relief pattern formed by the formation method of the hardening relief pattern of Claim 15.