TW201005002A - 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 DEG C or less. A polyamide resin used in the photosensitive resin composition is also disclosed. The polyamide resin contains structural units represented by formula (1) with a repetition number of 2-150 which is within the range of 80-100% of the total number of the structural units constituting the polyamide resin. [In formula (1), X represents a trivalent organic group having 6-15 carbon atoms; m represents 0 or 2; Y represents a divalent organic group having 6-35 carbon atoms when m = 0, and represents a tetravalent organic group having 6-35 carbon atoms when m = 2; and R1 represents an aliphatic group having at least one radically polymerizable unsaturated linking group with 5-20 carbon atoms, which may contain an atom other than carbon atoms.]

Description

[Technical Field] The present invention relates to an insulating material for an electronic component, a surface protective film for a semiconductor device, an interlayer insulating film, an α-ray shielding film, and the like, and can be used for mounting A polyimide resin having an image sensor, a micromachine or a microactuator, a conductor device, or the like, a photosensitive tree-containing fat composition containing the polyimide resin, and hardening using the photosensitive resin composition A method of forming a relief pattern, and a semiconductor device having the cured relief pattern. More specifically, the present invention relates to a photosensitive property at the time of exposure to ultraviolet light, which is excellent even if it is, for example, 200. (: A novel photosensitive polyamine resin which exhibits excellent heat resistance, chemical resistance, mechanical properties, and low residual stress characteristics under the following heat curing conditions, and a photosensitive resin composition containing the same, and the use of the photosensitive A semiconductor device manufactured by using a resin composition. [Prior Art] It is widely used for applications such as an insulating material for electronic components and a surface protective film, an interlayer insulating film, and an α-line shielding film for semiconductor devices, and has excellent heat resistance. A polyimine resin having electrical properties and mechanical properties. The resin is usually provided in the form of a photosensitive polyimideimine precursor composition, and is characterized in that it is applied to a substrate and passed through a patterned mask required; irradiated with active light (exposure) and developed, and then subjected to heat hardening (thermal imidization) treatment, whereby an embossed pattern composed of a heat-resistant polyimide resin can be easily formed (For example, refer to the following patent document 丨). In recent years, in the manufacturing steps of semiconductor devices, mainly due to the material and structural design aspects of the constituent members. The reason for the material that can be subjected to 140879.doc 201005002 heat hardening (thermal imidization) treatment at a lower temperature is increasing, but in the case of the prior art polyamidiene resin precursor composition, If the heat-hardening treatment temperature is lowered, the thermal imidization cannot be completed, and various physical properties are deteriorated. Therefore, the lower limit of the heat-hardening treatment temperature is at most about 3 〇 (rc). The company is also working on the polymer skeleton structure and composition additives. In order to maintain the practical properties of the polyimide film, it is considered to be about 25 〇t as a limit (see, for example, Patent Document 2 below). Therefore, it is not known in the art. The photosensitive property at the time of the ultraviolet-ray exposure is excellent, and it is set to 200. (The following is a photosensitive resin composition which is suitable for practical film characteristics under the heat hardening conditions. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. 2006/008991 [Patent Document 4] International Publication No. 2006/008991 [Invention 1] [Problems to be Solved by the Invention] Patent Document 3 discloses a photosensitive group via a guanamine group and a resin. The polyamine which is directly bonded to the skeleton is not disclosed in the patent document 4, but any of the above techniques is applied to the heat hardening (thermal imidization) treatment at a lower temperature. In order to solve the problem, it is possible to provide a resin film which is excellent in sensitivity and resolution even when it is formed by a low-temperature heat-hardening condition of, for example, 200 C or less. The resin film is provided with a polyamide resin and a photosensitive resin composition having excellent chemical properties. Further, the problem to be solved by the present invention is to provide a method for forming a cured embossed pattern using the photosensitive resin composition, and a semiconductor device having a cured embossed pattern formed by the method. [Means for Solving the Problems] The present inventors have made an effort to solve the above problems, and as a result, have found that the above problems can be solved by producing a photosensitive resin composition by using a polyamine which is produced from a specific raw material as a matrix. And the present invention is finally completed. Specifically, the present invention is as follows: [1] A polyamine resin which is in the range of 2 to 15 Å in the number of repetitions and which constitutes all of the polyamide resin A structural unit represented by the following formula (1) is contained in a range of 80 to 100% of the total number of structural units, [Chemical Formula 1]

(1) In the formula, X is a trivalent organic group having a carbon number of 6 to 15, and 〇 is 0 or 2, and Y is a work. It is a divalent organic group having a carbon number of 6 to 35, and a tetravalent group having a carbon number of 6 to 35 when m=2, and may have an atom other than carbon and a carbon number of 5 to 2 Å having at least - 140879.doc 201005002 A radical group of a radical polymerizable unsaturated bond. [2] a polyamine-based resin which has a structure represented by the following formula (2) in such a manner that the total number of all the structural units of the polyamine-branched amine is 80% or more by the number of repetitions in the following formula (7). 2]

In the formula, X is a trivalent organic group having a carbon number of 6 to 15, 111 is ruthenium or 2, γ is a divalent organic group having a carbon number of 6 to 35 when m=〇, and a carbon number of 6 when m=2. The tetravalent organic group of ～35 is a two-valent organic group of carbon number 6 to 15 'k is an integer of 1 or more, and (n+k) is an integer of 5 to 150, and R1 may contain an atom other than carbon, and An aliphatic group having 5 to 2 carbon atoms having at least one radical polymerizable unsaturated bonding group. [3] A polyamine resin which has a structure represented by the following formula (3) as a constituent unit. The number of repetitions η in the above formula (3) is based on the total number of all structural units constituting the polyamide resin of 80 to 100. Within the range of %, [Chemical 3]

140879.doc • · (3) 201005002 (Formula Yin, X is a 3-valent organic group with a carbon number of 6 to 15, the claw is ruthenium or 2, and γ is a 2-valent organic group having a carbon number of 6 to 35 when m=〇, When m=2, it is a tetravalent organic group having a carbon number of 6 to 35, W is a divalent organic group having 6 to 15 carbon atoms, 1 is an integer of 1 or more, and (n+1) is an integer of 2 to 150. R1 may contain an aliphatic group having a carbon number of 5 to 2 Å having at least one radical polymerizable unsaturated bonding group. [4] Any one of the above [1] to [3] The polyamine resin wherein the above & is a group represented by the following formula (4): [Chemical Formula 4] sr N - Rj · - (4) {wherein, r2 has at least - (iv) fluorenyl polymerizability The polyamine resin of any one of the above [1] to [3] wherein the above & is at least one (meth) propylene oxime Oxymethyl group. 1

[6] The polyamine resin in any one of the above [1] to [3], wherein each of the above is independently selected from the group consisting of an aromatic group, an alicyclic group, an aliphatic group, an anthraquinone, and the like. a group of groups consisting of groups of composite structures. [7] A photosensitive resin composition comprising: (A) a mass fraction of the polyamide resin according to any one of the above [1] to [6] (B) a photopolymerization initiator 0.5 to 2 parts by mass . The photosensitive resin composition of the above [7], which further contains (b) 4 parts by mass of the (A) polyamine resin, and has photopolymerizability. A monomer that is unsaturated with a binder. [9] The photosensitive resin composition according to the above [7] or [8], which further comprises (D) a hot paternity in an amount of 丨 to (10) parts by mass based on 1 part by mass of the (A) polyamine resin. The compound (D) is preferably a compound which thermally crosslinks the above (A) polyamine resin or forms a compound having a heat crosslinked network structure. [1] The photosensitive resin composition according to the above [9], wherein the (D) thermally crosslinkable compound has an alkoxymethyl group as a thermally crosslinkable group. [11] The photosensitive resin composition according to any one of the above [7] to [1], further comprising 1 to 25 parts by mass based on 1 part by mass of the above (A) polyamine resin ( E) decane coupling agent. [12] The photosensitive resin composition according to [11] above, wherein the decane coupling agent is an organic dream compound having a (dialkoxy)monoalkylindenyl group or a (trialkoxy)indenyl group. [13] The photosensitive resin composition according to any one of the above [7] to [12] further comprising: 〇i~1〇 of the mass of the above (Α)polyamine resin (F) a benzotriazine sitting compound. [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 method of forming a hardened embossed pattern, comprising: applying a photosensitive resin composition according to any one of the above [7] to [13] or a photosensitive resin composition as described above in Π 4] a step of forming a coating on a substrate 140879.doc 201005002 a coating film of a photosensitive resin composition; an exposure step of irradiating the coating film with active light directly or via a patterned mask; a developing step of dissolving and removing the exposed portion to form a embossed pattern; and a step of heat-hardening the embossed pattern to form a hardened embossed pattern. [16] A semiconductor device having a hardened relief pattern formed by a method of forming a hardened relief pattern as described above. [Effects of the Invention] The polyimide resin of the present invention and the photosensitive resin composition containing the same can provide a resin film which exhibits excellent (iv) chemical properties even under low-temperature heat curing conditions of, for example, two thieves. The present invention also provides a method of forming a cured embossed pattern excellent in chemical resistance of (4) a photosensitive resin composition, and a semiconductor device having a cured embossed pattern formed by the method. [Embodiment] Hereinafter, the present invention will be specifically described. In addition, in the case of a plurality of singularities in the present invention, the structure represented by the same reference numeral may be one type or a combination of two or more types. <Polyurethane Resin> An aspect of the present invention provides a polyamide resin in which the number of repetitions is in the range of 2 to 150 and the number of repetitions reaches 80 of the total number of all structural units constituting the polyamide resin. ～1〇〇% of the range includes the following 140879.doc 201005002 The structural unit represented by the formula (1): [Chemical 5]

Ri • · *(1) {wherein, X is a trivalent organic group having a carbon number of 6 to 15, m is 0 or 2, and (4) is a divalent organic group having a carbon number of 6 to 35, and a carbon number of 6 (4). The valence of ～35 is a group of aliphatic groups having at least one radical polymerizable unsaturated bond group which may contain a carbon number of 5 to 2 Å of an atom other than carbon. W: 1 is in /, ~...<The number of repetitions of the structural unit of Mi wind meter i is 2 to 15 〇, and if the number of repetitions is 2 or more, if the number of repetitions is the necessary condition for the polymer as expected in the present invention, it is repeated. When the number is 150 or less, it is preferable in terms of solubility in a diluent solvent or a material speed in development treatment when a photosensitive resin composition is prepared. The above-mentioned number of repetitions of the structural unit represented by the above formula (1) is more preferably 2 to 1 Å. Further, in the present specification, the number of repetitions of the structural unit refers to the number of structural units present in the i molecule, and the structural unit may be continuously repeated or repeated with other structural units. In the present aspect, among all the structural units constituting the polystyrene resin, the ratio of the number of repetitions of the structural unit represented by the above formula (1) is within the range of 80 to H). When the above ratio is 8% by weight or more, the photosensitive property of the coating film formed by the photosensitive (tetra)m composition of the present invention can be raised to the extent expected by the invention of 140879.doc -10- 201005002, who./± ^ ^ ^ Further, the mechanical properties of the coating film after heat curing can be excellent in heat resistance and chemical resistance to the extent expected by the present invention. The above ratio is preferably 85% or more. The structural unit of the polyamide resin may be only the structural unit represented by the above formula (1) (that is, the above ratio is 1 嶋) from the viewpoints of the photosensitive property, the heat resistance, and the chemical resistance, but in order to further improve The adhesion between the various constituent materials that are in contact with each other during the formation of the semiconductor element, or the various properties are imparted to it, and it is also preferable that the polyamine has a structure other than the crucible unit represented by the above (1). In this case, the above ratio is 20% or less, preferably 15% or less. In the case where the number of repetitions of the structural unit represented by the above formula (1) is 2 and 3, the number of repetitions is 100% of the total number of all structural units constituting the polyamide resin. According to another aspect of the present invention, there is provided a polyamine resin which is contained in such a manner that the repeating number n in the following formula (2) reaches 80% or more of the total number of all structural units constituting the polyamide resin The structure represented by the formula (2): [Chem. 6]

In the formula, X is a trivalent organic group having a carbon number of 6 to 15, m is 0 or 2, and Y is a divalent organic group having a carbon number of 6 to 35 when m=〇, and a carbon number of 6 when m=2. ~35 of the 4 price organic 140879.doc •11- 201005002 The base 'W is the carbon number 6~15 of the two-valent organic group, k is an integer of 1 or more, and (n+k) is an integer of 5~150, Rl is An aliphatic group having a carbon number of 5 to 2 Å having at least one radical polymerizable unsaturated bond group other than carbon. In the above formula (2), the arrangement of the structure of the repeating number n and the structure of the number of repetitions k may be random or block. In the formula (2), k is an integer of 1 or more, and (n+k) is an integer of 5 to 15 Å. By making k 1 or more, an effect of causing the various structures represented by the number of repetitions to be copolymerized is obtained. In the meantime, when (n+k) is 5 or more, it satisfies the requirements for the polymer which is expected in the present invention, and if (n+k) is 15 Å or less, the dissolution solvent is dissolved in the preparation of the photosensitive resin composition. It is preferable in terms of properties, rapidity in development processing, and the like. (n+k) is preferably 5 to 1 〇〇. In the total number of all the structural units constituting the polyamine resin, the number of the structural units having the number of repetitions n in the above formula (2) (that is, the ratio of ... is 80% or more. If the ratio is 8 G% or more Further, the photosensitive property of the coating film formed of the photosensitive resin composition of the present invention can be improved to the extent expected by the present invention, and the mechanical properties, heat resistance and chemical resistance of the coating film can be improved by heat curing. The above-mentioned ratio is preferably 85% or more. In the present aspect, among the total number of all the structural units constituting the polyamide resin, the number of the structural units of the number of repetitions k in the above formula (2) The ratio of (i.e., k) is 20% or less. When the ratio is 2% or less, excellent photosensitive properties, mechanical properties, heat resistance, chemical resistance, and semiconductor formation at the same time can be ensured. The various 140879.doc 201005002 contacted during the process of the component constitutes the adhesion between the materials, and can impart various characteristics as desired. The above ratio is preferably 15% or less. From the viewpoints of optical properties, mechanical properties, heat resistance, and chemical resistance, the polyamine resin of the present aspect may have only the structure represented by the above formula (2) as a structural unit, or may have a formula (2) In the case of the structural unit represented by the above formula (丨) or (2), when the terminal of the polyamine resin of the present invention is a structural unit represented by the above formula (丨) or (2), the molecular chain end is derived from the inclusion of a carboxyl group of a trivalent organic dicarboxylic acid or an amine group derived from a diamine having a divalent or tetravalent organic group represented by γ; but the polyamine resin in this aspect may also be a chemical modification of the carboxyl group (eg, esterified, amide, etc.) and various chemical modifications of the amine (eg, amide, urethane, guanidinium, etc.). Another aspect of the invention provides the following Polyamine resin: the structure represented by the following formula (3) is used as a structural unit, and the number of repetitions η in the above formula is in the range of 80 to 1% by weight of all structural units constituting the polyamide resin. Inside, [7]

〇

LrL(A«)m (3) {wherein, X is a trivalent organic group having a carbon number of 6 to 15, 111 is () or 2, and a melon = a divalent organic group having a carbon number of 6 to 35, sm =2 is the carbon number 6~35 of the 4 price shoulder 140879.doc -13- 201005002 base, w is the carbon number 6~15 of the two-valent organic group, 1 is 〇 or an integer of 1 or more simultaneously (n+l) An integer of 2 to 150, and the core is an aliphatic group having 5 to 20 carbon atoms which may have a radical polymerizable unsaturated bonding group of an atom other than carbon. Further, the arrangement of the structure of the repeating number n and the number of repeating numbers in the above formula (3) may be random or block. (n+1) in the formula (3) is 2 to 15 Å, and if (n+1) is 2 or more, the desired condition as a polymer of the present invention can be satisfied, if (η + ι) is 15 In the case where the photosensitive resin composition is prepared, it is preferable in terms of solubility in the solvent #, and rapidity in development processing. The above-mentioned number of repetitions of the structural unit represented by the above formula (3) is preferably 2 to the structural unit represented by the repeating unit n in the total number of all structural units constituting the polyamide resin in the present aspect. The ratio of the number of repetitions is in the range of 80 1 〇〇〇 / 0. When the ratio is more than or equal to the above, the photosensitive property of the coating film formed from the photosensitive resin composition of the present invention can be improved to the extent expected by the present invention, and further, the mechanical properties and heat resistance of the coating medium after heat curing can be achieved. It is excellent in properties and chemical resistance to the extent expected by the present invention. The above ratio is preferably 85% or more. From the viewpoints of photosensitivity, heat resistance, resistance, and susceptibility, the structural unit of the polyacrylamide resin may be only a structural unit represented by repeating Tcn (the ratio of η is 1% by weight), but In-- strict 0 liters. It is also preferable to have a structural unit represented by the repeating unit 1 in the case where various constituent materials which are in contact with each other during the formation of the semiconductor element, or various characteristics are provided as needed, and in this case, The rate is 20/〇 or less, preferably 15% or less. If the structure of the repeating unit 1 is set to 20°/ of the total number of all structural units. In the following, I40879.doc • 14 - 201005002 can ensure the photosensitive characteristics and mechanical properties, heat resistance and chemical resistance of the present invention, and can impart various characteristics required Q (11+1) is 2 to 4 In the case, the structural unit represented by the repeating unit η reaches 1 〇〇〇/0 of the total number of all structural units constituting the polyamide resin.

The molecular chain end of the polyamide resin in this aspect is derived from a rebel group containing a carboxylic acid of a trivalent organic group represented by another, or a rebel from a taulic acid containing a divalent organic group represented by w. a group or an amine group derived from a diamine having a divalent or tetravalent organic group represented by γ, but may also be various chemical modifications (for example, an esterified product, a amide amide, etc.) of the carboxyl group, and the amine group Various chemical modifications (eg, amides, urethanes, guanidines, etc.). In the above formulae (1) to (3), &> is an aliphatic group having 5 to 2 carbon atoms having at least one radical polymerizable unsaturated bonding group which may contain an atom other than carbon. From the viewpoints of photosensitivity and chemical resistance, Ri is preferably a group represented by the following formula (4): [Chem. 8]

Ο Η || I R2 * * · (4) {wherein R 2 is an aliphatic group having 4 to 19 carbon atoms having at least one radical polymerizable unsaturated bonding group}. Further, in terms of further improving the photosensitive characteristics, it is preferable to have a group having at least one (meth)acryloyloxymethyl group. In the above formulas (1) to (3), the trivalent organic group represented by fluorene is a carbon number of 6 from the viewpoints of sensitivity, mechanical properties, heat resistance, chemical resistance, and the like. 15% organic base. In the formulae (1) to (3), the divalent or valence organic group represented by γ is an organic group having a carbon number of 6 to 35 in terms of photosensitivity, mechanical properties, heat resistance, chemical resistance and the like. Further, the divalent organic group represented by W in the formulas (7) and (3) is a divalent organic group having 6 to 15 carbon atoms from the viewpoints of photosensitivity, mechanical properties, heat resistance, chemical resistance and the like. Further, w is a structure in which a moiety derived from two slow groups is removed from the structure of a dibasic acid or a derivative thereof. In the present invention, in view of photosensitivity, mechanical properties, heat resistance, chemical resistance, and the like, the above w, χ & γ are preferably independently selected from the group consisting of an aromatic group, an alicyclic group, and an aliphatic group. a group consisting of a group, a decyloxy group, and a group of such composite structures. In the above formulae (1) to (3), X is further preferably an aromatic group selected from the group consisting of the groups represented by the following structures: [Chemical 9] ▼ poor and further preferably self The amino group is substituted with an aromatic group of a group 'and an amine group in the structure of the isophthalic acid. In the formulae (1) to (3), hydrazine is further preferably a cyclic organic group having 1 to 4 substituted aromatic or aliphatic rings, or an aliphatic group or a stone having no cyclic structure. Oxygen burnt base. Preferred examples of the above cyclic organic group include the following aromatic group or alicyclic group: 140879.doc -16- 201005002 [Chemical]

140879.doc 17 201005002 [化il]

(wherein A is independently a group selected from the group consisting of a hydroxyl group, a methyl group, an ethyl group, a propyl group and a butyl group, and the propyl group and the butyl group also contain various isomers). 140879.doc -18- 201005002 [Chem. 12]

{wherein, p and q are each independently an integer of 〇~3' r is an integer of 〇~8, s and t are each independently an integer of 〇10, and B is a methyl group, an ethyl group, a propyl group, a butyl group or These isomers}. In the above formula, p and q respectively represent the number of repeats of the fluorenylene chain 'r, s&t respectively represent the number of substitutions of the substituent B on the ring and B represent a substituent on the ring, especially the carbon number* Hydrocarbyl group. Further, as a preferred example of the aliphatic group or the oxime group having no cyclic structure, the following groups are exemplified: 140879.doc •19· 201005002 [Chem. 13]

In the formula, a is an integer of 2 to 12, b is an integer of 1 to 3, and c is an integer of 1 to 20', and R3 and R4 are each independently an alkyl group having a carbon number of 33 or a phenyl group which may be substituted. }. W in the formulae (7) and (3) is preferably an aromatic group, a lipid group or an alicyclic group. Preferred examples of the aromatic group include the following groups: 140879.doc -20. 201005002 [Chem. 14]

The polyamine resin of the present invention is synthesized in the following manner, for example, the synthesis of a phthalic acid compound end-capping material is first made to have a trivalent aromatic group intercalated along the disk, +, 々4 | a compound of the corresponding group of ruthenium, for example, selected from the group consisting of phthalic acid substituted with an amine group, phthalic acid substituted with an amine group, and terephthalic acid substituted with an amine group One or more kinds of compounds (hereinafter referred to as "the phthalic acid 140879.doc -21 - 201005002 compound") 1 moles are reacted with one or more kinds of compounds which react with the amine group, and the synthesis is carried out. One or more of the following compounds containing a radical polymerizable group and a bond group to modify and block the amine group of the phthalic acid compound (hereinafter referred to as "benzoic acid compound terminator"). The structure in which the above-mentioned radical-polymerizable unsaturated bond-containing group terephthalic acid compound is blocked can impart a negative photosensitive property (i.e., photocurability) to the polyamide resin. From the viewpoint of the photosensitive property and the chemical resistance, the group containing a radical polymerizable unsaturated bond is preferably an aliphatic group having a carbon number of 5 to 20 containing a radical polymerizable unsaturated bonding group, particularly preferably It is an aliphatic group containing a methyl propylene oxymethyl group and/or an acrylonitrile group. The above-mentioned phthalic acid compound end-capture can be obtained by using an amine group of a phthalic acid compound and an aliphatic helium gas or an aliphatic isocyanine having a carbon number of 5 to 20% having at least one radical polymerizable unsaturated bonding group. It is obtained by reacting a vinegar or an aliphatic epoxy compound. As the suitable aliphatic ruthenium chloride, 2 - [(meth) propylene oxime] oxime, 3 - [(meth) propylene oxime] propionyl chloride, 2-[(methyl) propyl Grafting oxy]ethyl carboxylic acid vinegar, 3 · [(indenyl) propylene oxypropyl] carbamic acid ester and the like. As suitable aliphatic isocyanic acid, 2-(meth) propylene methoxyethyl isocyanate, bis[(methyl) propylene fluorenyloxy] isocyanate, isocyanide Acid 2_[2-(methyl)acryloxyethoxyethoxy]ethyl ester or the like. As a suitable aliphatic epoxy compound, (methylamide) glycidyl acrylate is mentioned. These may be used singly or in combination of two or more. It is especially preferred to use 2-methylpropenyloxyacetic acid isocyanate. Further, in the phthalic acid compound end cap, since the stearic dicarboxylic acid compound is 5-aminoisophthalic acid, it is possible to obtain a polyamine which is excellent in photosensitive characteristics and has excellent film properties after heat curing and 140879.doc -22· 201005002. Resin, so the above-mentioned end-capping reaction is better, and the dicarboxylic acid compound can be sealed with a gypsum in the presence of a tin-based catalyst such as a thief or a tin-based catalyst such as dibutyltin dilaurate. The terminal agent is stirred and dissolved in a reaction solvent and mixed. As the reaction solvent, it is preferred to completely dissolve the benzoic acid compound end-capping product which is a product of rabbit, for example, it can be wrapped. N-methyl-2-pyrrolidinium, N, N-di Methylacetamide, N, N-dimethylamine, dimercapto, tetramethylurea, γ-butyrolactone, and the like.

As for the reaction solvent, in addition to the above, it is exemplified by ketones, esters, internal vinegars, ethers, dentate hydrocarbons and hydrocarbons, and examples thereof include acetone and methyl ethyl ketone. , methyl isobutyl ketone, cyclohexanone, acetic acid, ethyl acetate, acetic acid butyl vinegar, oxalic acid diethyl acetonate, ethylene glycol dimethyl _, diethylene glycol dimethyl riding, tetrahydro hydrazine Qijiayuan, U2_di-ethane, m_di-butane, gas benzene, o-dibenzene, hexane, heptane, stupid, toluene, and diphenylbenzene. These solvents can be used separately as needed. Two or more types may be used in combination. The type of the blocking agent such as helium gas may generate hydrogenated hydrogen during the end-capping reaction. In this case, it is also preferable to prevent contamination of the subsequent steps. Purification is carried out as appropriate: the product is temporarily reprecipitated by water and washed with water, or passed through a column packed with an ion exchange resin to reduce the removal of ionic components, etc. The synthesis of the polyamine resin is second, The above phthalic acid compound end-caption and having a divalent or tetravalent organic group Y (with the above formula The diamine compound corresponding to γ is mixed in a suitable solvent in the presence of a basic catalyst such as pyridinium or diethylamine in the presence of a basic catalyst such as pyridine or diethylamine to carry out polycondensation of the guanamine. The polyamine resin of the present invention is obtained. If necessary, a part of the benzoic acid compound endblock may be replaced with a diacid having a divalent organic group W (a group corresponding to w in the above formula) In combination, it is preferred that the ratio of the structure of the phthalic acid compound end-capping material to the total number of all the structural units of the polyamidamide resin is 80% or more and 100% or less. In view of the combination ratio, the photosensitive property at the time of ultraviolet exposure and the film property after heat hardening, particularly chemical resistance, can be raised to the level expected in the present invention. The method of polycondensation of the above-described guanamine can be exemplified by a method of mixing a monocarboxylic acid component (a phthalic acid compound endblock and a dicarboxylic acid having a divalent organic group W, the same below) with a diamine compound by using a dehydrating condensing agent; using a known method A method of mixing a dicarboxylic acid component with a monoamine compound after gasification; a method of mixing a product with a diamine compound after reacting the dicarboxylic acid component with an active esterifying agent in the presence of a dehydrating condensing agent to carry out active esterification As a preferred dehydrating condensing agent, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-epethoxy-1,2-dihydroquinoline, carbonyldi Oxy-di-b-benzotriazole, ^^^-dipodoximine imino carbonate, etc. Examples of the gasifying agent include sulfinium chloride and the like. As for the active esterifying agent, there may be mentioned :N-hydroxysuccinimide, hydroxybenzotriazole, N-hydroxy-5-northene-2,3-dicarboxylic acid quinone imine, 2-hydroxyimino-2-cyanoacetic acid Ester, 2-hydroxyl iminyl 2-cyanoacetamide, and the like. 140879.doc •24· 201005002 As the dicarboxylic acid having a divalent organic group W, phthalic acid, isophthalic acid, terephthalic acid, 4,4 nonyldiphenyl ether dicarboxylic acid, 3,4'-diphenyl ether dicarboxylic acid, 3,3·-diphenyl ether dicarboxylic acid, 4,4·-diphenyl phthalic acid, 3,4′-diphenyl phthalic acid, 3,3 fluorene biphenyl Dicarboxylic acid, 4,4'-dibenyldicarboxylic acid, 3,4·-benzophenone dicarboxylic acid, 3,3·-benzophenone dicarboxylic acid, 4,4′-hexafluoroisopropylidene Diphenyl decanoic acid, 4,4·-dicarboxydiphenyl decylamine, 1,4-phenylenediacetic acid, iota, bis-(4-carboxyphenyl)-1-phenyl_2,2, 2-trifluoroethane, bis(4-carboxyphenyl) sulfide, bis(4-carboxyphenyl)tetraphenyldioxane, bis(4-carboxyphenyl)tetramethyldioxane, Bis(4-carboxyphenyl)anthracene, bis(4-carboxyphenyl)decane, 5-t-butylisophthalic acid, 5-indolizine, 5-fluoroisophthalic acid, 5 - isophthalic acid, 4-isophthalic acid, 5-hydroxyisophthalic acid, 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, N_(3,5•2 Carboxyphenyl)_N, _ ethoxy Carbonyl urea, (3,5-dicarboxyphenyl) norbornene quinone imine, 2,2-bis(p-carboxyphenyl)propane 4,4 (p-styldioxy)dibenzoic acid, 2, An aromatic dibasic acid such as 6-naphthalene dicarboxylic acid; in addition to the following: succinic acid, adipic acid, octanoic acid, hydrazine-acid, fumaric acid, maleic acid, An aliphatic dicarboxylic acid and an alicyclic dicarboxylic acid such as malic acid, hexanedicarboxylic acid, M•cyclohexanedicarboxylic acid, and % of olefin-2,3-dicarboxylic acid. As the diamined human sulfonate containing the organic group γ, it is preferably selected from the group consisting of an aromatic monoamine compound, an aromatic bisamine, a mu 肸# 埘化, and an alicyclic diamine. The chain is known to be a diamine compound and a group of diamine compounds which are composed of a small amount of alkanediamine compound, which can be used in combination with φ + $ ^ V; Wang Yufang's aromatic diamine compound, exemplified by: p-phenylenediamine, diphthene 140879.doc -25- 201005002 amine, 4,4'-diaminodiphenyl ether, 3,4'-diamine Diphenyl ether, 3,3'-diaminodiphenyl mystery, 4,4 匕diaminodiphenyl sulfide, 3,4'-diamino-mono-thioether, 3,3 '-Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl hydrazine, 3,4'-diaminodiphenyl sulfone, 3,3.-diaminodiphenyl hydrazine, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4' -diaminobenzophenone, 3,3,-diaminobenzophenone, 4,4'-diaminodiphenylnonane, 3,4.-diaminodiphenylmethane, 3 , 3·-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, iota, 3-bis(4-aminophenoxy)benzene, 1,3-double ( 3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]anthracene, 4,4' - bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, Bis[4-(3-aminophenoxy) Ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl) stupid, 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-amine-based aryl)phenyl]hexafluoropropanone, 1,4-bis(3-aminopropyldiaphthalenyl)benzene, o-linked Toluidine, 9,9-bis(4-aminophenyl)anthracene, and a portion of the hydrogen atoms on the benzene rings are selected from the group consisting of fluorenyl, ethyl, hydroxymethyl, benzyl and methoxy A diamine compound substituted with at least one or more of the group consisting of. As an example of the diamine compound in which the hydrogen atom on the benzene ring is substituted, 3,3'·dimethyl-4,4·-diaminobiphenyl, 2,2,-dimethyl group is exemplified. 4,4,-Diaminobiphenyl, 3,3,-dimethyl-4,4'-diaminodiphenylmethane, 2,2,-dimethyl-4,4'-diamino Diphenylmethane, 3,3,-dimethoxy_4,4,diamine linkage 140879.doc • 26- 201005002 Benzene, 3,3'-digas _4,4,-diamine linkage Benzene, etc. As the aromatic bisamine compound, there may be mentioned: 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-dihydroxy- 4,4'-diaminodiphenyl hard, bis(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-phenylphenyl)propane, 2, 2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, bis(3-hydroxy-4-amino group Phenyl)methane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 3,3,-dihydroxy-4,4'-diaminobenzophenone, 3 3ι_ Hydroxy-44, diaminodiphenyl ether, 4,4'-dihydroxy-3,3'-diaminodiphenyl ether, 2,5-dihydroxy-1,4-diaminobenzene, 4 , 6-diaminoresorcinol, 151_bis(3-amino-4-ylhydroxyphenyl)cyclohexane, 4,4-(α-methylbenzylidene)-bis(2-amino Phenol) and the like. As the alicyclic diamine compound, there may be mentioned diamine cyclopentane, 1,3-diaminocyclohexane, iota, 3-diaminomethylcyclohexane, and 3,5-diamino group. -1,1-dimethylcyclohexane, 15-diamino-. , dinonylcyclohexane, 1,3,diamino-1-indenyl-4-isopropanylcyclohexane, 1,2-diamino-4-methylcyclohexene, 1,4- Diaminocyclohexanone, iota, 4-diamino 2,5-diethylcyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(amino group) Base) cyclohexane, 2-(3-aminocyclopentyl)_2-propylamine, menthane diamine, iSOph〇rone diamine, norbornadiene diamine ( Norbornane diamine), 1-cycloheptene_3,7-diamine, 4,4'-methylenebis(cyclohexylamine), 4,4'-arylene di(2-methylcyclohexylamine) , 1,4-bis(3-aminopropyl) piperculating, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro-[5,5]- Undecane and the like. As the linear aliphatic diamine compound, 1,2-diaminoethane 140879.doc •27·201005002, 1,4-diaminobutane, anthracene, 6-diaminohexane, Hydrocarbon type diamine such as 18-diaminooctane, 1,10-monoamine oxime, 1,12-diamino-12; 2-(2-aminoethoxy)ethylamine, 2 An oxidized exo-diamine such as 2,-(ethylenedioxy)diethylamine or bis[2(2aminoethoxy)ethyl]ether. As the oxane diamine compound, dimethyl (poly) decane diamine, for example, trade names of PAm_E, KF-8010, X-22-161A, etc. manufactured by Shin-Etsu Chemical Co., Ltd. can be mentioned. As the reaction solvent, it is preferred to completely dissolve the produced polymer; for example, N-methyl-2-guanidine, n,N-dimethylacetamide, and glutamine, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, γ-butyrolactone, and the like. In addition, ketones, esters, lactones, ethers, hydrocarbons, and southern hydrocarbons may be used as a reaction solvent, as the case may be. Specific examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate ethylene glycol dimethyl ether, and Ethylene glycol dimethyl ether, tetrahydrofuran, di-halogen methane, U2_di-ethane, 込'dioxane, chlorobenzene, o-diphenyl, hexane, heptane, benzene, toluene, diphenyl Wait. After completion of the polycondensation reaction of the guanamine, the precipitates derived from the dehydrating condensing agent, which are precipitated in the reaction liquid, are optionally subjected to filtration separation. Then, a non-"good solvent" of polyamine which is water or an aliphatic lower alcohol or a mixed solution thereof is introduced into the reaction liquid to precipitate polyamine. Further, by repeating the operation of re-dissolving the precipitated polyamine in a solvent and precipitating and precipitating it, purification is carried out, and vacuum drying is carried out to separate the target polyamine. Further, in order to further improve the degree of pureness of 140879.doc -28- 201005002, the solution of the polyamide may be passed through a column packed with an ion exchange resin to remove ionic impurities. The polystyrene-equivalent weight average molecular weight obtained by gel dialysis chromatography (hereinafter referred to as "GPC") of the polyamide resin of the present invention is preferably 7,000 to 70,000, and more preferably 1 Å. ~5〇〇〇〇. When the weight average molecular weight in terms of polystyrene is 7,000 or more, the basic physical properties of the cured embossed pattern are good. Further, when the weight average molecular weight in terms of polystyrene is 70,000 or less, the development solubility in forming a relief pattern is good.

As a solution of GPC, tetrahydrofuran and N-methyl-2-pyrrolidinone are recommended. Further, the weight average molecular weight value was determined based on a calibration curve prepared by using a standard monodisperse polystyrene. As a standard monodisperse polystyrene, it is recommended to select from the standard SM-105, an organic solvent standard sample manufactured by Showa Denko. <Photosensitive Resin Composition> The present invention also provides (A) 100 parts by mass of the above polyamine resin of the present invention (hereinafter also referred to as (A) polyamide resin), and (B) photopolymerization 0.5 to 20 parts by mass of the photosensitive resin composition of the starting agent. The specific aspect of the (A) polyamine resin which can be used in the photosensitive resin composition of the present invention is as described above. In the photosensitive resin composition of the present invention, the above-mentioned (A) polyamine resin and (B) photopolymerization initiator are used in combination with respect to the viewpoint of imparting photosensitivity. (B) Photopolymerization initiator As the (B) photopolymerization initiator, any of the previously known compounds as a polyamidophotopolymerization initiator can be used. As a preferred example, for example, 140879.doc -29- 201005002: [1] benzophenone, methyl phthalate, 4-phenylidene _4, _methyl diphenyl a benzophenone derivative such as a ketone, a dibenzyl ketone or an anthrone; [2] 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2- Dimethoxy-1,2-diphenylethane-1-one, hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(indolylthio)phenyl]-2-morpholinyl Propane-ketone, 2-hydroxy-l-{4-[4-(2-hydroxy-2-f-propylpropenyl)benzyl]phenyl-2-methylpropan-1-one, phenylacetaldehyde An acetophenone derivative such as methyl ester; [3J9-oxopurine p-star, 2-methyl-9-oxothiop-purin, 2-isopropyl-9-oxosulfonate, diethyl 9-oxo-sulfur-u-p-star derivative of -9-oxo-p-p-p-star, etc. [4] benzil, benzil-di-f- ketone, benzophenone _β_ 曱 oxygen a benzoyl hydrazine derivative such as an acetal; [5] a benzoin derivative such as benzoin, benzoin methyl ether, 2-hydroxy-2-methyl-phenylpropanone, etc. [6] 1-phenyl- 1,2-butanedione_2·(〇_methoxycarbonyl)肟,丨·phenyl-L2-propanyl-2—(〇- Oxycarbonyl)diphenyl, 1-phenyl-1,2-propanedione-2-(anthracene-ethoxycarbonyl)anthracene, 1-phenyl-1,2-propanedione-2-(0-benzene Mercapto) ι, ι, 3-diphenyl glycerin-2-(0-ethoxycarbonyl) fluorene, 1-phenyl _3 ethoxy propyl ketone-2-(0-benzoquinone醯基), 12-octanedione, 丨#^phenylthio)_,2 (nonylphenylhydrazine), ethyl ketone, 1-[9-ethyl-6-(2-mercaptobenzene)曱醯基)_9H-味峻_ 3-yl]-, 1-(〇_乙醯基肟) and other lanthanide compounds; [7] 2-hydroxy_2·methyl-1-phenylpropane_1 -ketone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-indol-1-propan-1-one, 2-hydroxy-1-{4_[4_(2_ Heart hydroxy ketone of hydroxy-2-methylpropionyl)benzyl]phenyl b-2-ylpropanepropane 140879.doc -30- 201005002 Compound; [8] 2benzyl 2-methylamino group 4 (4-morpholinylphenyl)butanone oxime, dimethylamino 2-(4-methylbenzyl) smear (4) oxalin 4-ylphenyl) butyl sylvestre Ketone compound; [9] bis(2,4,6-dimethylbenzylidene)phenylphosphine oxide, bis(26-dimethoxybenzoyl)-2,4'4-tri Methylpentylphosphine oxide, 2, 4 a phosphine oxide compound such as 6_trimethylbenzimidyl-diphenylphosphine oxide; [1〇] bis(η5-2,4-cyclopentaphenanthyl).bis (26_2) A ferrocene compound such as fluorine_3 (1 Η | ΐ 略 略 - )) phenyl) titanium or the like. Further, these photopolymerization initiators may be used singly or in combination of two or more kinds as needed. Among the above photopolymerization initiators, in particular, in terms of light sensitivity, it is further preferred to be an anthracene of [6]. The amount of the photopolymerization initiator to be used is preferably from 0.5 to 2 parts by mass, more preferably from 1 to 10 parts by mass, per 100 parts by mass of the (poly)polyamide resin. When the amount of the above-mentioned compounding amount is 5% by mass or more, "a radical which can sufficiently accelerate the photoradical polymerization during exposure" can ensure a sufficiently good light sensitivity in practical use, and thus it is possible to obtain a practically suitable light sensitivity. Embossed pattern. Moreover, when the amount of the above-mentioned compounding amount is 20 parts by mass or less, when the substrate coated with the photosensitive resin composition is exposed, the exposure light can be favorably reached to the vicinity of the substrate surface, and thus the film thickness direction can be obtained. Uniform photoradical polymerization is carried out to obtain a embossed pattern suitable for practical use. (C) The monomer having a photopolymerizable unsaturated bond is used to improve the photosensitive property such as sensitivity and resolution. The photosensitive resin composition of the present invention may further comprise (C) a photopolymerizable unsaturated bond. • 31 - 201005002 Monomer. The (c) monomer having a photopolymerizable unsaturated bond is preferably a (meth)acrylic compound which can be subjected to radical polymerization using the above (B) photopolymerization initiator, and examples thereof include polyethylene. Diol diacrylate (each ethylene glycol unit number is 2~20), polyethylene glycol dimethacrylate (each ethylene glycol single 7L number is 2~20), poly(1,2-propanediol) II Acrylate, poly(12-propylene glycol) dimercapto acrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, glycerin diacrylate, glyceryl dimethacrylate, dipentaerythritol hexaacrylate, fluorenylene dimercapto Amine, N-hydroxydecyl acrylamide, ethylene glycol diglycidyl ether _ methacrylic acid adduct glycerol condensate _ hydroglyceryl ether-acrylic acid adduct, bisphenol A diglycidyl ether _ acrylic acid A product, a bisphenol A diglycidyl ether decyl acrylate adduct, N,N-bis(2-methylpropoxy oxyethyl) urea, and the like. These may be used alone or in combination of two or more. (C) The monomer having a photopolymerizable unsaturated bond is preferably 1 to 4 parts by mass, more preferably 1 to 20 parts by mass based on 1 part by mass of the (A) polyamine resin. Share. When the amount of the above-mentioned compounding amount is i parts by mass or more, photocrosslinking (photoradical polymerization) of the exposed portion can be sufficiently performed at the time of exposure, and Q can be ensured to be sufficiently good in practical use. Practical embossed pattern. Further, when the amount of the above-mentioned compounding amount is 40 parts by mass or less, unnecessary photohardening of the unexposed portion due to leakage of light from the exposed portion, that is, residue after development can be suppressed, and a suitable relief can be obtained. pattern. Further, it is preferable to suppress the residual monomer component which is an outgas component from the hardened film even when the low-temperature curing is performed. (D) Thermally crosslinkable compound 140879.doc • 32· 201005002 The photosensitive resin composition of the present invention may further comprise (D) a thermally crosslinkable compound in order to enhance film properties (especially heat resistance) after heat curing. . (D) The thermally crosslinkable compound is a compound which thermally crosslinks (A) a polyamide resin or a compound which forms a heat crosslinked network structure by itself. As the (D) thermally crosslinkable compound, a compound having an alkoxymethyl group as a heat crosslinking group, such as an amine resin or a derivative thereof, is suitably used. Among them, urea resin, glycoluril resin, hydroxyl extended ethyl urea resin, melamine resin, benzoguanamine resin, and the like are preferably used. Particularly preferred is hexamethoxymethylated melamine. The blending amount of the (D) thermally crosslinkable compound relative to (a) the polyamide component is preferably from 1 to 20 parts by mass, and more preferably from 3 to 15 parts by mass. When the amount of the above-mentioned compounding amount is 1 part by mass or more, the film properties of the photosensitive resin composition of the present invention after heat curing can be further improved. In the case where the amount of the compound is 20 parts by mass or less, the residual monomer component which is an outgas component from the cured film can be suppressed even when the temperature is hardened. (E) decane coupling agent In order to improve the photosensitivity such as adhesion during development, it is preferred that the photosensitive resin composition of the present invention contains (E) a decane coupling agent. As the (E) oxime, the alkane coupling agent is preferably an organic ruthenium compound having a (dialkoxy)monoalkylindenyl group or a (trialkoxy)stone group, and is, for example, represented by the following formula Compound: [Chem. 15] 140879.doc 33· 201005002

In the formula, g is an integer of 1 or 2, when g is 1, 2 is a divalent aromatic group, when 2 is 2, Z is a tetravalent aromatic group, and G is a carbon atom containing a bond directly bonded to a ruthenium atom. The divalent organic group, d is an integer of 0 or 1, Rs is a hydrogen atom or a hydrocarbyl group, R6 and R·; each independently is a carbon number of 1 to 4, and 6 is an integer of bite 1 }. The above decane coupling agent can be obtained by using a (dialkoxy) monoalkyl sulfhydryl compound having an amine group or a dimer emulsion or a tetrabasic acid dianhydride and a derivative thereof. Obtained by the reaction of the substance. As the dicarboxylic anhydride or the tetracarboxylic dianhydride and the derivative thereof, various structures can be used, and examples thereof include maleic anhydride, phthalic acid, hydrazine, 2 - cyclohexane dicarboxylic anhydride, and 4 _Indolylcyclohexane-1,2-dicarboxylic anhydride, cyclohexene _ 1,2_-formic anhydride, 5-reduced dilute-2,3-dicarboxylic acid, 1,2-naphthalene dicarboxylic acid needle 1,8-naphthalic anhydride, pyromellitic dianhydride, 3 3,4 4, benzophenone tetracarboxylic acid monoanhydride, 3,3',4,4'-diphenyl stone tetracarboxylic acid Xuan, 2,2-bis (3,4-di-rebase) hexafluoroisopropylidene tetraphthalic acid dianhydride, 3,3,,4,4'-diphenyl ether tetracarboxylic dianhydride, hydrazine, 2,] 〆-cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3,4,4'-diphenyltetracarboxylic dianhydride, and the like. Among them, phthalic anhydride and 3,3,4,4,-benzophenone tetraphthalic acid dianhydride are particularly preferable in view of the effect and price of excellent adhesion to the underlying substrate. 140879.doc -34- 201005002 As the (di-alkoxy) pre-alkyl group-based compound and the (tri-oxooxy) fluorenyl compound having an amine group, various structures can be used, and examples thereof include the following (hereinafter, The expression of alkoxy is methoxy or ethoxy): 2-aminoethyltrialkoxydecane, 3-aminopropyltrialkoxydecane, 3-aminopropyltrialkoxymethyl矽, 2-aminoethylaminomethyltrialkoxide, 2-aminoethylamino fluorenyl ruthenium oxanthine, 3-(2-aminoethylaminopropyl) Trialkoxy decane, 3-(2-aminoethylaminopropyl) di-sinter-oxymethyl sulphate, 3-dphthylpropyl propyl tris-oxygen oxide, 2_(2-amine ® ethyl ethionylethyl) trialkoxy decane, 2-(2-aminoethylthioethyl) dialkoxymethyl oxime, 3-piperidinyl propyl trialkoxy decane, 3_ Piperidinyl propyl secondary oxymethyl decane, cyclohexylaminopropyl trialkoxy decane, and the like. Particularly preferred is 3-aminopropyltriethoxydecane when considering the effect and price of the adhesion to the underlying substrate. Other than the above, the above-mentioned (dialkyloxy)monoalkylsulfonyl compound and (trialkoxy)indenyl compound having an amine group can be directly used as a decane coupling agent. Further, N-trialkoxyindenyl-anthracene and analtriazole, N-trialkoxycarbazide, N-trialkoxydecylpyrrole, N-trialkoxydecylpyridine, N-trialkoxydecyl pyrrolidine, piperidinylmethyltrialkoxydecane, 2-piperidylethyltrialkoxydecane, 3-morpholinylpropyltrialkoxydecane, 3_0 Bottom-propyl propyl trioxy decane, 3-piperidinyl propyl trialkoxy decane, 3-(4-mercaptopiperidyl propyl) trialkoxy decane, 3_(4·methylperazine Iridylpropyl)trialkoxydecane, 4-(2-trialkoxymercaptoethyl)pyridine, N_(3_s alkoxymercaptopropyl)-4,5-dihydroimidazole, 2-( 2-Trialkyloxyguanidinoethyl) 140879.doc -35- 201005002 ° Heterocyclic organic ruthenium compound such as pyridine or N-(3-trialkyloxymercaptopropyl). Further, a vinyl trialkoxy decane, a 1-propenyltrialkoxy oxime 2-propenyl bis-oxyxanthine, a 3-methyl propylene oxypropyltrisyloxy decane, 3-propenyl methoxypropyl trialkoxy decane, 3-methylpropenyl methoxypropyl methyl dialkoxy decane, 3-propylene propylene oxypropyl methyl dialkoxy decane, p-styryl An alkoxy decane, p-(p-propenylphenyl)trialkoxydecane, an organic ruthenium compound containing a carbon-carbon unsaturated bond such as (2-propenylphenyl; > trialkoxydecane. There may be mentioned: 2-(3,4-epoxycyclohexyl)ethyltrialkoxydecane, 3-glycidoxypropyltrialkoxydecane, 3-glycidoxypropylmethyl-oxygen Broken, p-phenylethenyl trioxylated calcined, N_(2-aminoethyl)-3-aminopropyltrialkoxydecane, N-(2-aminoethyl)_3_ Aminopropylmethyldialkoxydecane, 3-trialkoxyindenyl_N_(1,3-diindenyl-butylene)propylamine, N-phenyl-3-aminopropyltri Oxygen oxysaliline, 3_glycosyl propyl oxalate, sulphate, 3-glycosyl propyl dimethyl alkoxy Xizhuo, 3_ mercaptopropyl di-burning calcined base, 3-disylpropylmethyldioxalate, bis(trialkoxypropylpropyl) tetrasulfide, 3-isocyanate Propyl propyl trioxide oxyzepa sulphate, 6-trisyloxy acyl-2-reduced, di-oxy oxydoxylmethyl sulphur, 3-(three-sodium oxysyl) Base cyanoic acid anhydride, n-(3-di- oxymethylmethylmethyl propyl propyl sulfoxide, N-[3-(trimethyleneoxy) propyl] phthalic acid, N-[3-(Trialkyloxyindolyl)propyl] o-phenyleneimine, N-[3-(dioxaoxycarbonyl)propyl]phthalimide, etc. ( E) the decane coupling agent 'may be a single one or a mixture of two or more types. 140879.doc -36- 201005002. (E) the amount of the decane coupling agent relative to the (A) polyamine resin ι It is preferably 25 parts by mass and more preferably 2 parts by mass. When the amount of the above-mentioned compounding amount is 〇] by mass or more, the effect of improving the sensitivity of the photosensitive resin to the underlying substrate (four) is good. Further, when the above compounding amount is 25 parts by mass or less, the photosensitive resin combination is used. Since the silicon in the silane coupling agent Peter & dark reaction caused by the precipitation of substantially reduced fear (F) benzotriazole-based compound saliva.

In order to improve the adhesion of the photosensitive resin on the substrate (especially the copper substrate) or to suppress the discoloration of the copper substrate, it is preferred that the photosensitive resin composition of the present invention contains (F) a benzotriazole system. Compound. As the benzotriazole-based compound, for example, benzotriazole, bis(2-ethylhexyl)aminomethyl]benzotriazine, 4 (or 5)-rebel benzotriazole, 4(or 5)-methylbenzotriazole, 1-[Ν,Ν_bis(2-ethylhexyl)aminomethyl]_4(or 5)-methylbenzotriazole, 1-[Ν , Ν-bis(hydroxyethyl)aminomethyl]_4 (or 5)-fluorenyl benzoic acid, hydroxy decyl benzotriazole, 1-[(2-ethylhexylamino)methyl] Stupid triazole, 1-(1,2,-dicarboxyethyl)benzotriazole, N_benzotrienylmethylurea, 2,6-bis[(1H-benzotriazole- 1-yl) fluorenyl] 4-methylbenzene, 1-(2,3-dicarboxypropyl)benzotriazole, 2-t-butyl-4-methyl-6-[(1H-benzene) And triazol-1-yl)indolyl]phenol, 2,4-di-t-butyl-6-[(1Η-benzotris-l-yl)methyl]phenol, 4 (or 5)- Nitrobenzotriazole and the like. Of these, 'excellent is 4 (or 5)-rebel benzotriene" sit, 4 (or 5)-methylbenzotriazole. (F) The benzotriazole-based compound may be used alone or in a mixture of two or more. (F) benzotriazole-based compound relative to (A) polyamine resin 1 enamel 140879.doc -37· 201005002 The amount of the component is preferably in parts by mass, and more preferably 〇5~5 Parts by mass. When the amount of the above-mentioned compounding amount is 0.1 part by mass or more, the adhesion of the photosensitive resin on the substrate (especially the copper substrate) can be improved, and the effect of suppressing discoloration of the copper substrate can be favorably exhibited. In addition, when the amount of the above-mentioned compounding is 10 parts by mass or less, the decrease in the adhesion of the photosensitive resin on the substrate (especially the steel substrate) can be suppressed. Other components: sensitizer The photosensitive resin composition may further contain a sensitizer for enhancing the light sensitivity, as needed. As such a sensitizer, for example, rice ketone, 4,4'-bis(diethylamino)benzhydrazide' 2,5•bis(4,_diethylamino) can be mentioned. Alkyl) cyclopentanone, 2,6-bis(4,-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-didecylaminobenzylidene)-4- Methylcyclohexyl-, 26-bis(4,diethylaminobenzylidene)-4-methylcyclohexanone, 4,4,-bis(dimethylamino)chalcone, 4,4' - bis(diethylamino)chalcone, 2_(4'-dimethylamino cinnamic acid) fluorenone, 2-(4·-diamidinobenzylidene) fluorenone, 2_( _4,_Dimethylaminobiphenyl)benzothiazole, 1,3-bis(4-dimethylaminobenzylidene)acetone, !,3-bis(4-diethylamino) Benzylene)acetone, 3,3,-yl-bis(7-diethylaminocoumarin), 3-ethoxyethyl-7-dimethylaminocoumarin, 3-ethoxylate Carbonyl-7-diamidyl coumarin, 3-benzyloxycarbonyl-7-dimethylamino coumarin, 3-methoxylated-7-diethylamino coumarin, Ethoxy ethoxy-ethylamine glucoside, N-phenyl hydrazine-ethylethanolamine, N-phenyldiethanolamine , Ν-p-tolyldiethanolamine, hydrazine-phenylethanolamine, quinone bis(2- 1%ethyl)amine, 4-mercapto-benzonitrile, 4-dimethylaminobenzoic acid Amyl ester, isoamyl 4-diethylaminophenyl benzoate, hydrazine, 2,3-benzotriene 140879.doc -38 * 201005002 Jun, 2-mercaptobenzimidazole, fluorene-phenyl-5-fluorenyl -^, Anus sinensis, anthracycline-5-mercapto-1,2,3,4-tetrazole, 1-(t-butyl)-5-fluorenyl", tetrabendazole Benzothiazole, 2-(p-dimethylaminostyryl) benzoxazole, 2·(p-dimethylaminostyryl)benzothiazole, (p-dimethylaminostyryl) Naphthoquinone (l,2-p)carbazole, 2-(p-dimethylaminobenzoyl)styrene, etc. The sensitizer used may be a single one or a mixture of two or more kinds. The amount of the sensitizer is preferably from 0 to 15 parts by mass, and more preferably from 1 to 1 part by mass, based on 1 part by mass of the (A) polyamine resin. Other components: polymerization inhibitor It is necessary to improve the viscosity of the photosensitive resin composition solution and the stability of the light sensitivity during storage. The polymerization inhibitor composition may further contain a polymerization inhibitor. Examples of such a polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, and p-tert-butyl catechol. , phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol myuric acid tetraacetic acid, 26_digastric tert-butyl- p-Methylphenol, 5-nitrosohydroxyquinoline, arginyl-2-naphthol' 2-nitroso-1.naphthol, 2-nitroso-5-(N-ethyl_N_ Sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N_nitroso-N_phenylhydroxylamine ammonium salt, N-nitrosonaphthyl)hydroxylamine ammonium salt, Bis(4-carbo-3,5-di-t-butyl)phenylpyrene or the like. The amount of the polymerization inhibitor is preferably from 0 to 5 parts by mass, more preferably from 1 part by mass, per 100 parts by mass of the (A) polyamine resin. When the amount of the above-mentioned compounding amount is 5 parts by mass or less, the desired light is not inhibited. 140879.doc -39- 201005002 The crosslinking reaction is well ensured, and the light sensitivity suitable for practical use can be satisfactorily ensured. In the photosensitive resin composition of the present invention, various additives such as a human scattering light absorber coating smoothness imparting agent may be appropriately blended as needed in addition to the above. <Photosensitive resin composition solution>

The present invention also provides a photosensitive resin composition solution comprising the photosensitive resin composition of the present invention and a solvent. It is preferred to use a photosensitive resin composition solution in which the viscosity is adjusted by adding a solvent to the photosensitive resin composition. As a suitable solvent, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethyl B Indoleamine, dimethylhydrazine, hexamethylsulphonamide, pyridine, cyclopentanone, γ-butyrolactone, α-ethenylbutyrolactone, tetradecylurea, dimethyl-24 saliva. The ketone, N-cyclohexyl-2-material (tetra), etc. may be used singly or in combination of two or more. Particularly preferred among these are i-methyl-2-pyrrolidone and γ-butyrolactone. These solvents may be according to the coating medium thickness and viscosity of the photosensitive resin composition solution.

The inductive resin composition towel to be added to the present invention is preferably used in an amount of from 1 to 1 part by mass based on 100 parts by mass of the (poly)polyamide resin. In addition to the above, in addition to the above, the following alcohols may be used in combination with the above-mentioned additives. The alcoholic group is not particularly limited as long as it has an alcoholic hydroxyl group in the molecule, and examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tributylsulfonate. , section _, lactic acid ethyl acetate, lactic acid butyl propylene glycol single 140879.doc -40- 201005002 propylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol monoethyl ether, hydrazine, propylene glycol mono (n-propyl) , propylene glycol di(n-propyl) shout, ethylene glycol monomethyl i-ethylene glycol monoethyl test, ethylene glycol mono (n-propyl) oxime, B, etc., especially good - alcohol early benzene wire, Monools such as ethylene glycol monohydrate, H diethylene glycol monophenylhydrazine, etc.; glycols such as ethylene glycol and propylene glycol are used in combination with ethylene glycol and ethylene glycol monophenyl ether (4). The content ratio of the alcohol in the solution (tetra) is preferably 50% by mass or less. When the ratio exceeds 5 〇% by mass, the solubility of the (4) polyamine resin in the solvent tends to decrease. <Method of Forming Hardened Emboss Pattern> The present invention also provides a method of forming a hardened embossed pattern, comprising: coating the above-described photosensitive resin composition of the present invention or the photosensitive resin composition solution of the present invention a step of forming a coating film of the photosensitive resin composition on the substrate, and exposing the unexposed portion of the coating film to the coating film by exposing the active film to the coating film directly or via a patterned mask. a developing step of forming a embossed pattern; and a step of heat-hardening the embossed pattern to form a hardened embossed pattern. Hereinafter, an example of a method of forming the cured relief pattern of the present invention will be described. First, the photosensitive resin composition or the photosensitive resin composition solution of the present invention is applied onto a substrate such as a ruthenium wafer, an aluminum substrate or a copper substrate. As the coating device or the coating method, a spin coater, a slit press coater, a spray coater, a dipping, a printing, a knife coater, a roll coating method, or the like can be used. The coating film is dried by prebaking at 80 to 120 ° C, and the film of the photosensitive resin is combined to form a film having a film thickness of about 5 to 5 μm. 140879.doc 201005002 Next, using a contact projection device such as a contact aligner, a mirror projection exposure machine, a stepper, etc., the active film is irradiated to the formed film directly or via a desired patterned mask (mask). Thereby, the coating film is exposed. As the active light, X-ray, electron beam, ultraviolet light, visible light or the like can be used. In the present invention, it is preferred to use active light having a wavelength of 200 to 500 nm. After the exposure, in order to improve the light sensitivity and the like, a combination of any temperature and time may be employed as needed (preferably, the temperature is 4 〇β (: 〜12 〇 it, time is 10 seconds to 240 seconds). Post-baking or pre-development baking. The development of the embossed pattern is formed by dissolving and removing the unexposed portion of the coating film by a developing solution. The developing method may be a self-dipping method, a mixing method, a rotary spray method, or the like. The method is selected as the developer, and a good solvent of polyamine can be used alone or a good solvent of polyamine can be suitably used as a poor solvent. As a good solvent, methylpyrrolidone or ethyl ketone can be used. -2-pyrrolidone, N,N_: mercaptoacetamide, N,N-dimercaptoamine, monomethyl; ε, γ·butyrolactone, α-ethenylbutyrolactone, Cyclopentamin, cyclohexanone, etc.; and as a poor solvent, toluene, dioxane benzyl alcohol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, water, etc. may be used. When a good solvent is mixed with a poor solvent, the mixing ratio is based on the use The solubility of the polyamine resin, the development method used, etc. are adjusted, for example, 'the use of an aromatic bisaminophenol as the divalent or tetravalent organic γ used in the polyamine resin of the present invention. When all of the diamine compound or a part of 140879.doc •42· 201005002, an aqueous solution can be used as the developer. As an aqueous solution, sodium hydroxide, sodium carbonate, sodium citrate, ammonia, etc. can be used. An aqueous solution of an inorganic test, an aqueous solution of an organic amine such as ethylamine, triethylamine, triethylamine or triethanolamine, or a tetrabasic salt such as tetramethylammonium hydroxide or tetrabutylphosphonium hydroxide. Water-soluble nights and, as needed, add appropriate amounts of water-soluble organic solvents such as methanol and ethanol, and surfactants to the water-soluble nights. After the development, use the eluent as needed. The developer is removed 'by this to obtain a relief pattern. As the eluent, steamed water, methanol, ethanol, isopropanol, toluene, dimethoprim, propylene glycol monomethyl ether acetate, propylene glycol monomethyl can be used alone. Ether, etc. Two or more types may be used in combination as appropriate, or two or more types may be used in combination. The embossing pattern of the polyamidamine obtained in this manner is appropriately heated to, for example, 150 to 350 C'. Heat hardening and cross-linking reaction, thereby converting into a hardened relief pattern formed by polyamine which is excellent in heat resistance and chemical resistance. This heat-hardening treatment can use a hot plate, an oxidation-free oven, and a settable temperature. It is carried out by a temperature-increasing oven, etc. As the ambient gas during heat curing, air may be used, or an inert gas such as nitrogen or argon may be used. <Semiconductor device> The present invention also provides a semiconductor device having a a cured embossed pattern formed by the method for forming a cured embossed pattern of the present invention. The cured embossed pattern produced in the above manner is used as a surface protective film of a semiconductor device on a substrate such as a stone wafer. Interlayer insulating film. The ray shielding film, the partition wall, the barrier rib, and the like are used. In other steps, a well-known method of manufacturing a semiconductor device is employed, whereby a semiconductor device can be manufactured. Further, a semiconductor device having a coating film composed of a resin obtained by curing the photosensitive resin composition of the present invention described above can be obtained. [Examples] Hereinafter, the present invention will be described using examples and comparative examples. In addition, the combination of the polymer raw materials of the respective synthesis examples is shown in the following table. [Synthesis Example 1] (Synthesis of phthalic acid compound end-capped AIPA-MO) In a separable flask having a capacity of 5 liters, 543 5 g (3 〇mol) of 5-amino-based stearic acid was introduced. Hereinafter, N_mercapto-2-pyrrolidone {hereinafter referred to as ΑϊρΑ}, 17 〇〇g {hereinafter referred to as ^^11>}, was stirred and heated to 50 C in a water bath. Diluted 512.0 g (3.3 m〇i) of 2_methacryloyloxyethyl isocyanate with 500 g of γ-butyrolactone {hereinafter referred to as GBL} by using a dropping funnel. The solution was stirred at 5 〇ac for about 2 hours in this state. After the reaction was completed by low molecular weight gel dialysis chromatography (hereinafter referred to as low molecular weight GpC) (5-aminoisophthalic acid disappeared), the reaction solution was poured into 15 liters of ion-exchanged water and stirred. After standing, the crystal precipitate of the reaction product was awaited and separated by filtration, and after appropriate washing with water, it was vacuum dried at 4 ° C for 48 hours, thereby obtaining an amine group of 5-aminoisophthalic acid and isocyanic acid 2 - AIPA-MO formed by the isocyanate action of methacryloxyethyl ester. The low molecular weight GPC of the obtained AIPA-MO was approximately 100% pure. [Synthesis Example 2] 140879.doc 201005002 (Synthesis of phthalic acid compound end-capped AIPA-BA) In a separable flask having a capacity of 5 liters, 543.5 g (3.0 mol) of AIPA and 1700 g of NMP were charged. Mix and stir, heat to 50 ° C in a water bath. In this case, 789.46 g (3.3 mol) of 1,1 - bis(acryloxymethyl)ethyl isocyanate was diluted with 500 g of GBL by using a dropping funnel, and in this state, 50 Stir at °C for about 2 hours. After confirming the completion of the reaction (AIPA disappearance) by low molecular weight GPC, the reaction solution was poured into 15 liters of ion-exchanged water, stirred, and allowed to stand, waiting for the crystal precipitation of the reaction product, and filtering and separating, and appropriately washing with water, 4 (vacuum drying under TC for 48 hours, thereby obtaining the AIPA-BA formed by the isocyanate group of the amine group of AIPA and the 1,1-bis(acrylofluorenyl)ethyl isocyanate. The low molecular weight of the obtained AIPA-BA The purity of GPC is approximately 100%. [Synthesis Example 3] (Synthesis of phthalic acid compound end-capping AIPA-ΜΕ) In a separable flask having a capacity of 5 liters, 543.5 g (3.0 mol) of AIPA and 1700 g were charged. NMP, mixed and stirred, heated to 50 ° C in a water bath. In this, using a dropping funnel, add 657.38 g (3.3 mol) of isocyanic acid 2-(2-methylpropene oxime) to 500 g of GBL. The diluted solution of ethoxy)ethyl ester was stirred at 50 ° C for 2 hours in this state. After confirming the completion of the reaction (AIPA disappearance) by low molecular weight GPC, the reaction solution was poured into 15 liters of ion exchange water. Stirring, standing, waiting for the reaction product The crystals were precipitated and separated by filtration, and after appropriate washing with water, vacuum drying at 40 ° C for 48 hours, thereby obtaining an amine group of AIPA and isocyanic acid 140879.doc -45 - 201005002 2-(2-methacrylofluorene oxide AIPA-ME formed by the isocyanate group reaction of ethoxy)ethyl ester. The purity of the low molecular weight GPC of the obtained AIPA-ME is approximately 100%. [Synthesis Example 4] (Synthesis of phthalic acid compound end product AIPA-NBI) In a separable flask having a capacity of 5 liters, 543.5 g (3.0 mol) of AIPA and 1700 g of NMP were charged, mixed and stirred, and heated to 50 ° C in a water bath, in which a drop was added using a dropping funnel to 500. GBL of g. A solution of 541.73 g (3.3 mol) of 5-northene-2,3-dicarboxylic anhydride was diluted, and stirred at 50 ° C for about 1 hour in this state. The reaction was confirmed by low molecular weight GPC. Completion (AIPA disappears), and further confirmed by FT-IR (Fourier Transform-InfraRed) spectroscopic analysis that the imidization of the decyl quinone is completed (carboxy group disappears), and the reaction solution is poured into 15 liters of ion-exchanged water. And stirring, standing, waiting for the crystal precipitation of the reaction product and The mixture was separated by filtration, washed with water, and dried under vacuum at 40 ° C for 48 hours, whereby an amine group of AIPA and an acid anhydride group of 5-northene-2,3-dicarboxylic anhydride were obtained to form a decylene oxime. The imine structure of AIPA-NBI. The low molecular weight GPC of the obtained AIPA-NBI is approximately 100% pure. [Synthesis Example 5] (Synthesis of phthalic acid compound terminator AIPA-MA) In a separable flask having a capacity of 5 liters, 543.5 g (3.0 mol) of AIPA and 1700 g of NMP were charged and mixed and stirred. In this case, a solution diluted with 344.97 g (3.3 mol) of methyl 140879.doc • 46-201005002 acrylonitrile chloride was added dropwise with 500 g of GBL using a dropping funnel, and stirred at room temperature in this state. Hours or so. After confirming the completion of the reaction (AIPA disappearance) by low molecular weight GPC, the reaction solution was poured into 15 liters of ion-exchanged water, stirred, and allowed to stand, and the reaction product was crystallized and precipitated, and filtered, and washed at 40 ° as appropriate. It was vacuum dried for 48 hours at C, whereby AIPA-MA produced by the hydrazine group reaction of the amine group of AIPA and the methacrylium ruthenium chloride was obtained. The low molecular weight GPC of the obtained AIPA-MA was approximately 100% pure. • [Synthesis Example 6] (Synthesis of decane coupling agent S-1) In a round bottom flask having a capacity of 1 L, 32.2 g (0.1 mol) of 3,3',4,4·-benzophenone IV was added. Styric acid dianhydride and 206 g of NMP were started to stir. The solution was cooled to 〇 ° C while maintaining a solution of 100 g of NMP and 44.2 g (0.2 mol) of 3-aminopropyltriethoxydecane as a solution. After completion of the dropwise addition, it was returned to room temperature and stirred for 4 hours, whereby an acid anhydride group of 3,3',4,4'-benzophenonetetracarboxylic dianhydride and 3-aminopropyltriethoxysilane were obtained. 20-mass/(^^〇 solution of the decane coupling agent S-1 of the semi-acidified/semi-aminated amino group of the decyl group. [Synthesis Example 7] (Synthesis of decane coupling agent S-2) In a 1 L round bottom flask, 29-6 g (0.2 mol) of phthalic anhydride and 195 g of N-nonyl-2-pyrrolidone were added to start stirring. The solution was cooled to 0 ° C while maintaining 1 〇〇g of NMP was added dropwise to 4,200 g (0.2 mol) of 3-aminopropyltriethoxy decane. The solution was diluted 140879.doc -47- 201005002. After the addition was completed, Allowing it to return to room temperature and stirring for 4 hours, thereby obtaining a decanoyl coupling agent for reacting an acid anhydride group of phthalic anhydride with an amine group of 3-aminopropyltriethoxydecane to be a semi-acidified/semi-aminated 20% by mass of NMP solution of S-2 [Synthesis Example 8] (Synthesis of Polyamido PA-1) In a separable flask having a capacity of 2 liters, 100.89 g (0.3 mol) of Synthesis Example 1 was charged. Acquired AIPA-MO, 71.2 g (0.9 mol) Pyridine, 400 g of GBL and mixed, cooled to 5 ° C in an ice bath, in which 125 g of GBL was added dropwise over 20 minutes under ice bath cooling, 125.0 g (0.606 mol) of ruthenium, ruthenium-bicycle Hexylcarbodiimide {hereinafter referred to as DCC} Dissolve the diluted solution, followed by dropwise addition of 1 68 g for 20 minutes, 103.16 g (0.28 mol) of 4,4'-bis(4-aminophenoxy) a solution of biphenyl {hereinafter referred to as BAPB} dissolved while stirring at an ice bath for less than f ° C for 3 hours, followed by taking an ice bath and stirring at room temperature for 5 hours. Thereafter, the polycondensation process was carried out. The dicyclohexylurea (hereinafter referred to as DCU) derived from the dehydrating condensing agent was separated by filtration under pressure, and a mixture of 840 g of water and 560 g of isopropyl alcohol was added dropwise while stirring the filtrate (polymer solution). The precipitated polymer was separated and redissolved in 650 g of NMP. The redissolved droplets were added to 5 liters of ion-exchanged water under stirring to disperse the polymer, recovered, and washed at 40°. Drying under vacuum for 48 hours under C, thereby obtaining polyamidopatide PA-1. Polystyrene was measured by using NMP as a dissolving solution. GPC weight average molecular weight (column: Shodex KD-806Μχ2, NMP flow rate: 1.0 ml/min) is 34,700 ° 140879.doc -48- 201005002 [Synthesis Example 9] (synthesis of polyamido PA-2) in a capacity of 2 In a liter separable flask, 80.71 g (0.24 mol) of AIPA-MO obtained in Synthesis Example 1, and 19.64 g (0.06 mol) of AIPA-NBI and 71.2 g (0-9 mol) obtained in Synthesis Example 4 were charged. Pyridine, 400 g of GBL was mixed and then subjected to the same operation as in Synthesis Example 8, to obtain Polyamine PA-2. The polystyrene-converted GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 29,500. [Synthesis Example 10] (Synthesis of Polyamine PA-3) 80.71 g (0.24 mol) of AIPA-MO and 15.49 g (0.06 mol) of diphenylether-4,4'- obtained in Synthesis Example 1 were charged. Dicarboxylic acid, 71.2 g (0.9 mol) of pyridine, 400 g of GBL were mixed and cooled to 5 ° C in an ice bath. To this, 12 g of 125 g of GBL was added dropwise under ice-cooling for 20 minutes, 125.0 g (0.606 mol) of DCC was dissolved in the diluted solution, and then 168 g of NMP was added dropwise for 20 minutes to 121.1 g (0.28 mol) of the double. The solution of [4-(4-aminophenoxy)phenyl]sulfone dissolved was stirred for 3 hours while maintaining the temperature at 5 ° C in an ice bath, and then the ice bath was taken and stirred at room temperature for 5 hours. Then, the same operation as in Synthesis Example 8 was carried out to obtain Polyamine PA-3. The polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 32,000 ° [Synthesis Example 11] (Synthesis of Polyamine PA-4) Except that "103.16 g (0.28 mol) in Synthesis Example 8 "BAPB" replaces 140879.doc -49· 201005002 into "56.07 g (0.28 〇1)"| The remainder is the same as Synthesis Example 8. In the same manner as in the synthesis of Example 8 except for the 'diaminodiphenyl ether', the polyamine PA-4 was obtained. The molecular weight is 30,300. GPC weight average in terms of polystyrene conversion [Synthesis Example 12] (Synthesis of Polyamido PA-5) In addition to the "BAPB" body of "16 g (0·28 mo1) in Synthesis Example 8" 55.19 g (〇.26 m〇1) of 〇, ...^ _ , 2 -dimercapto-4,4,-diaminobiphenyl", the same operation as in Synthesis Example 8 was carried out, and Polyamine PA-5 was obtained. The polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 23,600. [Synthesis Example 13] (Synthesis of polyacrylamide PA-6) A synthesis example of 84 〇 8 g (〇 25 mol) was placed in a separable flask having a capacity of 2 liters! AiPA_M〇 obtained, 1〇i 35 g (〇75 m〇l) of 1-hydroxybenzodiazole, 39.6 g (〇.5 mol) of pyridine, 5.6 g (〇.〇5 mol) of 4- Dimethylamino"pyridinium, 275 g of N,N-dimethylformamide and mixed' was cooled to 5 in an ice bath. (:. Into the ice bath, use a 20-minute drop to add 134 lv, ^, dimethyl phthalamide, 134.11 § (〇.65 mol) of DCC dissolved in the diluted solution, and then Stirring was continued for 5 hours while maintaining the cooling of the ice bath. Thereafter, 48.81 g (〇.232 mol) of 4,4·-fluorenylene bis(cyclohexylamine) was dissolved in 146 g after 20 minutes of addition. a solution of dimercaptocarhamamine was stirred for 3 hours while maintaining the temperature at 5 ° C in an ice bath, and then the ice bath was removed and stirred at room temperature for 10 hours. 140879.doc -50- 201005002 Thereafter, The DCU precipitated during the polycondensation is subjected to pressure filtration separation, and a mixture of 1,000 g of water and 4,000 g of isopropyl alcohol is added dropwise while stirring the filtrate (polymer solution), and the precipitated polymer is separated and redissolved. In 800 g of NMP, the redissolved liquid droplets were added to 5 liters of ion-exchanged water under stirring to disperse and precipitate the polymer, which was recovered, washed with water, and dried under vacuum at 40 ° C for 48 hours. Polyamine PA-6. Polystyrene-converted GPC weight average molecule measured in the same manner as in Synthesis Example 8. 32,600. [Synthesis Example 14] (Synthesis of Polyamine PA-7) In a separable flask having a capacity of 1 liter, 47.9 g (0.2 mol) of the ruthenium-iridium, 31.6 obtained in Synthesis Example 2 was charged. g (0.4 mol) of pyridine, 147 g of NMP and mixed, and cooled to 5 ° C in an ice bath, and added thereto with an addition of 83 g of NMP to 83. 4 g under ice bath cooling for 20 minutes. 0.404 mol) of DCC dissolved the diluted solution, and then added about 6 minutes to dissolve 68.1 g (0.19 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane in 204 g of NMP. The solution was stirred for 3 hours while maintaining the temperature at 5 ° C in an ice bath, and then the ice bath was taken and stirred at room temperature for 10 hours. Thereafter, the DCU precipitated during the polycondensation was subjected to pressure filtration. Separation, while mixing the filtrate (polymer solution), a mixture of 760 g of water and 190 g of isopropyl alcohol was added dropwise, and the precipitated polymer was separated and redissolved in 400 g of NMP. The redissolved liquid was added to 3 liters of ion-exchanged water to disperse and precipitate the polymer, which was recovered, washed with water, and dried under vacuum at 40 ° C. 48 hours, thereby obtaining polyamine PA-7. The weight average molecular weight of the polystyrene-converted GPC measured by the same method as that of the synthesis of 140879.doc -51 - 201005002 was 8,600. [Synthesis Example 15] Synthesis of Amine PA-8) In a separable flask having a capacity of 2 liters, 114.11 g (0.3 mol) of ruthenium-iridium, 71.2 g (0.9 mol) of pyridine obtained in Synthesis Example 3, 400 g was charged. The GBL was mixed and thereafter subjected to the same operation as in Synthesis Example 8 to obtain Polyamine PA-8. The polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 33,000. [Synthesis Example 16] (Synthesis of Polyamine PA-9) Except that "103.16 g (0.28 mol) of BAPB" in Synthesis Example 8 was replaced with "4,4'-II of 28.04 § (0.14 111〇1) The same operation as in Synthesis Example 8 was carried out except that the aminodiphenyl ether and 29.72 g (0.14 mol) of 2,2·-dimethyl-4,4·-diaminobiphenyl were used to obtain a polyfluorene. Amine PA-9. The polystyrene-converted GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 28,200. [Synthesis Example 17] (Synthesis of Polyamine PA-10): In addition, "103.16 g (0.28 mol) of BAPB" in Synthesis Example 8 was replaced with "92.85 g (0.252 mol) of BAPB and 4.04 g (0.028 mol)". The same operation as in Synthesis Example 8 was carried out except that 1,8-diaminooctane was used to obtain polyamine PA-10. The polystyrene-converted GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 26,800. 140879.doc -52- 201005002 [Synthesis Example 18] (Synthesis of Polyamine PA-11) In a separable flask having a capacity of 2 liters, 100.89 g (0.3 mol) of AIPA obtained in Synthesis Example 1 was charged. MO, 71.2 g (0.9 mol) of pyridine, 400 g of GBL and mixed, and cooled to 5 ° C in an ice bath. To this, 12 g of 125 g of GBL was added dropwise under ice cooling for 12 minutes, and 125.0 g (0.606 mol) of DCC was dissolved in the diluted solution, followed by dropwise addition of 103.45 g (0.252 mol) of 2,2-double over 20 minutes. [4-(4-Aminophenoxy)phenyl]propanoid was dissolved in 168 g of NMP, and the mixture was stirred for 3 hours while maintaining the temperature at 5 ° C in an ice bath, followed by ice removal. The bath was stirred at room temperature for 5 hours. Thereafter, 36.4 g of the two terminal amine-modified polydimethyloxane, that is, the trade name KF-8010 manufactured by Shin-Etsu Chemical Co., Ltd. and 40 g of diethylene glycol dimethyl ether were mixed. And further stirred at room temperature for 5 hours. Then, the same operation as in Synthesis Example 8 was carried out to obtain Polyamine PA-11. The polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 28,000. [Synthesis Example 19] (Synthesis of Polyamido PA-12) In a separable flask having a capacity of 2 liters, 74.77 g (0.3 mol) of AIPA-MA, 71.2 g (0.9) obtained in Synthesis Example 5 was charged. Pyridine, 400 g of GBL and mixed, and cooled to 5 ° C in an ice bath. Among them, 12 g of 125 g of GBL was added dropwise for 20 minutes under ice-cooling, and 125.0 g (0.606 mol) of DCC was dissolved in the diluted solution, followed by dropwise addition of 56.07 g (0.28 mol) of 4,4'- over 20 minutes. Diaminodiphenyl ether was dissolved in 168 g of the solution of 140879.doc -53-201005002 NMP, while stirring at an ice bath for less than 5 ° C for 3 hours, then taking off the ice bath at room temperature Stir for 5 hours. Thereafter, the same operation as in Synthesis Example 8 was carried out to obtain Polyamine PA-12. The polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 29,500 ° [Synthesis Example 20] (synthesis of polyamido PA-13) in a separable flask having a capacity of 2 liters, 70.62 g (0.21 mol) of AIPA-MO, 14.95 g (0.09 mol) of phthalic acid, 71.2 g (0.9 mol) of ° ratio, 400 g of GBL and mixed, and then carried out and synthesis 8 The same operation was carried out to obtain polyamine PA-13. The polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 32,100 ° [Synthesis Example 21] (synthesis of polyamido PA-14) in a separable flask having a capacity of 2 liters, 60.53 g (0.18 mol) of ΑΙΡΑ-ΜΟ, 30·99 g (0.12 mol) of diphenyl ether-4,4,-didecanoic acid, 71.2 g (0.9 111〇1) ° bite, 400 g GBL was mixed, and then the same operation as in Synthesis Example 8 was carried out to obtain Polyamine PA-14. The polystyrene-equivalent GPC weight average molecular weight measured by the same method as in Synthesis Example 8 was 30,900. [Synthesis Example 22] (Synthesis of Polyimine Precursor PI-1) In a separable flask having a capacity of 5, 310.22 § (1.00 140879.doc - 54 - 201005002 〇1〇1) of diphenyl was charged. Ethyl ether-3,3',4,4'-tetracarboxylic dianhydride, 270.69 § (2.08 111〇1) methacrylic acid 2 - by base B, 158.2 g (2.00 mol) ° bite, 1000 GBL of g was mixed and stirred at room temperature for 16 hours. Into it, 400 g of GBL was added dropwise over 30 minutes under ice-cooling, 400.28 g (l.94 mol) of DCC was dissolved in the diluted solution, and then added in about 60 minutes to make 185.97 § (0.93111〇1) 4, Dispersion of 4'-diaminodiphenyl ether in 650 § GBL. The mixture was stirred for 3 hours while being cooled in an ice bath, and then the ice bath was taken and further stirred for 1 hour. The DCU precipitated in the polycondensation process was subjected to pressure filtration separation, and then the reaction liquid was added to 40 L of ethanol, and the polymer precipitated at this time was separated and washed, and vacuum-dried at 50 ° C for 24 hours. Thereby, the polyimine precursor PI-1 was obtained. The polystyrene-converted GPC weight average molecular weight measured under the same conditions as in Synthesis Example 8 was 29,000. [Example 1] 190 parts by mass of NMP was added to dissolve polyamine PA-1 with respect to 100 parts by mass of the polyamine PA-1 obtained in Synthesis Example 8, to prepare a crude solution having a pore diameter of 0.2 μm. The PTFE (polyfluoroethylene) filter was filtered to obtain a resin solution V-1. [Example 2] In addition to further adding 5 parts by mass of 1,3-diphenylpropanetrione-2-(0-ethoxycarbonyl) hydrazine as a photopolymerization initiator to the crude solution of Example 1, The rest was filtered in the same manner as in Example 1 to obtain a resin composition solution V-2. [Example 3] 140879.doc -55-201005002 In addition to the addition of 8 parts by mass of tetraethylene glycol dimethacrylate as a photopolymerizable monomer to the crude solution of Example 2, the same as in Example 1 Filtration was carried out in the same manner to obtain a resin composition solution v_3. [Example 4] The filtration was carried out 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 the crude solution of Example 3. Resin composition solution v_4. [Example 5] In addition to 5 parts by mass of the crude solution of Example 4, 20 masses of the decane coupling agent S-1 obtained in Synthesis Example 6 were further added. ANMP solution (pure s - 丨 is i by mass), 10 parts by mass of a 20% by mass NMP solution of decane coupling agent s_2 obtained in Synthesis Example 7 (pure S-2 is 2 parts by mass), and 5 parts by mass of 3- The mixture was filtered in the same manner as in Example 1 except for (trisyloxyindenyl)propyl succinic anhydride to obtain a resin composition solution V-5. [Example 6] A resin composition solution V-6 was obtained in the same manner as in Example 1 except that 2 parts by mass of 5-crude benzotriazole was further added to the crude solution of Example 5. . [Example 7] 5 parts by mass of 1,3-diphenylpropanetrione-2-(0-ethoxyl) was added to 100 parts by mass of the polyamine PA-1 obtained in Synthesis Example 8. Carbonyl) ruthenium, 8 parts by mass of tetraethylene glycol dimethacrylate, 5 parts by mass of hexamethoxymethylated melamine, and 5 parts by mass of 20% by mass of NMP of decane coupling agent s_ i obtained in Synthesis Example 6. Solution {pure 5-1 is 1 part by mass}, 10 parts by mass of synthesis 140879.doc • 56-201005002 decane coupling agent obtained in Example 7 § 2 of 2% by mass NMp solution {pure 2 parts by mass}, 5 Parts by mass of 3_(trialkoxymercapto)propyl succinic anhydride, parts by mass of 5-carboxybenzotriazole, 5 parts by mass; ^_bis(2-hydroxyethyl)aniline, 0.05 The nitrosodiphenylamine was dissolved in 19 parts by mass of hydrazine and filtered through a PTFE filter having a pore size of 0.2 μm to obtain a resin composition solution V_7. [Example 8] In addition to the polyamine pA-oxime used in Example 7 was replaced with PA-2 obtained in Synthesis Example 9, the 3-(trialkoxycarbonyl group) used in Example 7 was also similarly used. Resin composition solution V-8 was obtained in the same manner as in Example 7 except that propyl succinic anhydride was replaced with 3-glycidoxypropyl (dimethoxy) sulfhydryl. [Example 9] Except that the polyamine PA_i used in Example 7 was replaced with PA-3 obtained in Synthesis Example 1, the 3-(trialkoxycarbonyl group) used in Example 7 was also similarly used. Resin composition solution V-9 was obtained in the same manner as in Example 7 except that propyl succinic anhydride was replaced with 3-isocyanate propyl triethoxy oxime [Examples 10 to 17] The resin composition solution V- was obtained in the same manner as in Example 7 except that the polyamines pa-1 used in 7 were replaced with the polyamines PA-4 to PA-11 obtained in Synthesis Examples 11 to 18, respectively. 1 〇~V-17. [Comparative Examples 1 to 3] The polyamines PA-? which were used in Example 7 were replaced with the polyamines pa-12~PA-14 obtained in Examples 19 to 21, respectively, in the synthesis of 140879.doc-57-201005002. The resin composition solutions V'-1 to V, -3 were obtained in the same manner as in Example 7 except for the same. [Comparative Example 4] The polyamidoxime-1 used in Example 7 was replaced with the polyimine precursor ΡΙ-1 obtained in Synthesis Example 22, and the amount of the solvent oxime was adjusted to 165 parts by mass. The resin composition solution V'-4 was obtained in the same manner as in Example 7 except for the others. [Table 1]

Synthesis Example Polymeric acid 1 Acid 2 Diamine 1 Diamine 2 Synthesis Example 8 Examples 1 to 7 PA-1 AIPA-MO BAPB Synthesis Example 9 Example 8 PA-2 AIPA-MO (80) AIPA-NBI ( 20) BAPB Synthesis Example 10 Example 9 PA-3 AIPA-MO (80) DEDA (20) BAPS Synthesis Example 11 Example 10 PA-4 AIPA-MO DADPE Synthesis Example 12 Example 11 PA-5 AIPA-MO mTB Synthesis Example 13 Example 12 PA-6 AIPA-MO MBCA Synthesis Example 14 Example 13 PA-7 AIPA-BA 6FAP Synthesis Example 15 Example 14 PA-8 AIPA-ME BAPB Synthesis Example 16 Example 15 PA-9 AIPA-MO DADPE (50) mTB (50) Synthesis Example 实施 Example 16 PA-10 AIPA-MO BAPB (90) ODA (IO) Synthesis Example 18 Example 17 PA-11 ABPA-MO BAPP (90) KF8010 (10) Synthesis Example 19 Comparative Example 1 PA-12 AIPA-MA DADPE Synthesis Example 20 Comparative Example 2 PA-13 AIPA-MO (70) IPA (30) BAPB Synthesis Example 21 Comparative Example 3 PA-14 AIPA-MO (60) DEDA (40) BAPB Synthesis Example 22 Comparative Example 4 PI-1 ODPA BAPB Note: The values in the table (brackets) indicate the % of moles. Further, the above-mentioned undefined short names are as follows. 140879.doc • 58 · 201005002 ODPA : Diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride DEDC: diphenyl ether-4,4,-dioxane 0 ugly 0:diphenyl Ether-4,4'-dicarboxylic acid IPA: isophthalic acid BAPB: 4,4'-bis(4-aminophenoxy)biphenyl BAPS: bis[4-(4-aminophenoxy) Phenyl] bowl DADPE: 4,4'-diaminodiphenyl ether mTB: 2,2'-dimethyl-4,4'-diaminobiphenyl hydrazine]^«0 people: 4,4| -methylene bis(cyclohexylamine) 6FAP : 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane ODA : 1,8-octanediamine BAPP : 2,2-double [4 -(4-Aminophenoxy)phenyl]propane sensitization and adhesion evaluation during development were carried out by a spin coater (manufactured by Tokyo Electron, model name Clean Track Mark-8), Examples 2 to 17, and The resin composition solutions of Comparative Examples 1 to 4 were applied onto a 6-inch wafer and prebaked at 95 ° C for 4 minutes to obtain a coating film having an initial film thickness of 10 μm. Using an i-line stepper (manufactured by Nikon, model name: NSR2005i8A), the exposure mask was used to increase the exposure amount in the range of 100 to 1100 mJ/cm2 in increments of 50 mJ/cm2 each time. The film is exposed. After exposure for 30 minutes, cyclopentanone was used as a developing solution, and a coating film other than Example 13 was subjected to rotary jet development for a time until the unexposed portion was completely dissolved and disappeared by a time of 1.4, followed by propylene glycol monomethyl ether. The acetate was subjected to a spin-washing for 10 seconds to obtain an embossed pattern of 140879.doc • 59-201005002 composed of a resin film. With respect to the coating film of Example 13, after exposure for 3 minutes, a 2.38% aqueous solution (manufactured by AZ Elect_ic, product No. AZ-300MIF) of a tetrahydrogen hydroxide was used as a developing solution, and the unexposed portion was completely dissolved and disappeared. Multiply the time! The development of .4 was transferred, and then the water was rinsed by ion exchange water to obtain a relief pattern composed of a resin film. Observing the obtained embossed pattern under an optical microscope, and obtaining the minimum exposure amount (sensitivity) of the bright pattern which is not swollen, and the size (resolution) of the through hole (recessed rectangular pattern portion) when irradiated with the lowest exposure amount, Evaluation was made with the adhesion of the underlying layer (sexual ridge or peeling of the pattern). The results are shown in Table 2 below. Evaluation of Mechanical Properties The resin composition solutions of Example 17 and Comparative Examples 1 to 4 were applied to a 6-inch wafer previously vacuum-deposited with an aluminum thin film in the same manner as the evaluation of the above-mentioned photosensitive characteristics. , pre-baked, and then used a vertical hardening furnace (manufactured by Koyo Lindberg, model name VF_2〇〇〇B), and heat-hardened at 180 ° C for 2 hours under nitrogen atmosphere, and the film thickness after hardening was 10 A resin film of μιη. The resin film was cut into a thickness of 3 0 111111 by a dicing saw (manufactured by Disc ,, model name dAD_ ❹ 2H/6T), and it was immersed in a 1% hydrochloric acid aqueous solution to be peeled off from the ruthenium wafer. A film sample in the form of a ribbon. The film sample was allowed to stand in an environment of 23 C, 55% RH for 24 hours or more, and then the elongation of the film sample was evaluated in accordance with ASTM D-882-88 and subjected to a tensile test using a TENSILON (Universal Tensile Tester). The results are shown in Table 2 below. The heat resistance was evaluated by a thermomechanical analyzer (manufactured by Shimadzu Corporation, model name TMA-50). 140879.doc -60 - 201005002 The glass transition temperature (Tg) of the film sample prepared for the evaluation of the above mechanical properties was measured as a resin. The index of heat resistance of the film. The measurement conditions were as follows: the sample length was 10 mm, the constant load was 2 〇〇g/mm2, the measurement temperature range was 25 ° C to 450 ° C, and the temperature increase rate was 1 (rc/min, nitrogen atmosphere). The results are shown below. Table 2. Evaluation of residual stress The thickness of the "warpage amount" was measured in advance to be 625 μm 士 25 μπ ΐ 26 吋 吋 晶圆 晶圆 晶圆 ' 以 以 以 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布 涂布The resin composition solutions of Examples 1 to 4 were prebaked, and then subjected to a vertical hardening furnace (manufactured by K〇y〇Lindberg, model name VF-2000B) under a nitrogen atmosphere at 18 Torr. After the treatment, a crucible wafer having a resin film having a cured film thickness of μ0 μηι was prepared, and the residual stress of the wafer was measured by a residual stress measuring device (manufactured by Tencor Corporation, model name FLX 232 。). The results are shown below. Table 2. Chemical resistance evaluation The resin composition solutions of Example 17 and Comparative Example 4 were applied in advance by a spin coater (manufactured by Tokyo Electr〇n, model name ciean Track Mark-8). 3-aminopropyltriethoxydecane On a 6-inch wafer with underlying treatment, pre-bake at 95 ° C for 4 minutes to obtain a film with an initial film thickness of 10 μm. Using i-line stepper (Nik〇n, model) Name NSR2005i8A), the coating film is exposed by the evaluation mask under the condition of a fixed exposure amount, and the exposure amount is set to add the minimum exposure amount (sensitivity) of the vivid pattern which is not swelled in the evaluation of the above-mentioned photosensitive characteristics. 2〇〇140879.doc • 61- 201005002 mJ/cm. After exposure for 30 minutes, using cyclopentanone as a developing solution, the coating films other than Example 1 and Example 13 were applied until the unexposed portion was completely dissolved. The disappearing time was multiplied by a time of 1.4, and then spray-developed with propylene glycol monomethyl acetate for 10 seconds to obtain a relief pattern composed of a resin film. For the coating film of Example 13, After exposure for 3 minutes, a 2.38% aqueous solution of tetramethylammonium hydroxide (manufactured by Materials, manufactured by Materials, product number AZ_3〇〇MIF) was used as a developing solution, and the unexposed portion was completely dissolved and disappeared. Multiply the time by 14 Stirring development of the time, followed by spin water flow rinsing with ion-exchanged water to obtain a embossed pattern composed of a resin film. For the coating film of Example 1, since the coating film is not photosensitive, development is not performed. The spear J was subjected to a vertical hardening furnace (manufactured by K〇y〇Lindberg, model name VF_2000B), and the obtained embossed pattern film (Example 1 is an undeveloped flat film) was subjected to a hydrogen atmosphere at 180 C for 2 hours. The hardened embossed pattern film was produced by heat hardening treatment (Example 1 is a hardened flat film). A hardened film such as tantalum is heated by a photoresist stripping solution {manufactured by ATMI & Division, product name ST-44, main component of 2_(2-aminoethoxy)ethanol, 丨_cyclohexyl-2-pyrrolidone} The solution was immersed in the solution obtained at 85 C for 5 minutes, left to cool, and washed with running water β for 1 knives, and then air-dried. Thereafter, the surface of the film was visually observed under an optical microscope. The presence or absence of damage due to the chemical solution, such as cracks or sensitivities, or the film thickness change rate before and after the chemical solution treatment (unit: %, 1 〇〇 /. There is no change in film thickness, and 1% or more means swelling, and less than 1%% of the table 140879.doc 201005002 film dissolution) to evaluate chemical resistance. The results are shown in Table 3 below. Evaluation of copper discoloration after hardening The resin composition solutions of Examples 2 to 17 and Comparative Examples 1 to 4 were applied onto the following substrate by a spin coater (manufactured by Tokyo Electron, model name Clean Track Mark 8). Prebaking at 95 ° C for 4 minutes, and obtaining a coating film having an initial film thickness of 1 μm; the substrate is vacuum-deposited on a -6 inch wafer, and then steamed from above. A substrate obtained by subjecting copper to copper, followed by treatment with 3-aminopropyltriethoxydecane. • The coating film was exposed by an evaluation mask under the conditions of a fixed exposure amount using an i-line stepper (manufactured by Nikon, model name NSR2005i8A). The exposure amount is set to be 200 mJ/cm2 in which the minimum exposure amount (sensitivity) of the vivid pattern obtained by the evaluation of the above-mentioned photosensitive characteristics is not swollen. After exposure for 30 minutes, cyclopentanone was used as a developing solution, and the coating film other than Example 13 was subjected to rotary jet development until the time when the unexposed portion was completely dissolved and disappeared by multiplied by 1 _4, followed by propylene glycol monomethyl group. The ether acetate was spin-sprayed for 10 seconds to obtain an embossed pattern composed of a resin film. With respect to the coating film of Example 13, after exposure for 30 minutes, a 2.38% aqueous solution of tetrakisylammonium hydroxide (manufactured by AZ Electronic Materials, product No. AZ-300MIF) was used as a developing solution, and it was carried out until the unexposed portion was completely completed. The time during which the dissolution disappeared was multiplied by a time of 1.4, and then developed by a rotating water stream with ion-exchanged water to obtain a relief pattern composed of a resin film. Using a vertical hardening furnace (manufactured by Koyo Lindberg, model name VF-140879.doc -63·201005002 2000B), the embossed pattern on the obtained copper substrate was subjected to heat hardening treatment (curing) at 180 ° C under a nitrogen atmosphere. ), and a hardened relief pattern on the copper substrate is produced. The surface of the copper substrate of the unexposed portion was visually observed under an optical microscope, and the presence or absence of discoloration of the copper surface after hardening was evaluated. The results are shown in Table 3 below. [Table 2] Photosensitive property Mechanical property heat resistance residual stress (MPa) Sensitivity resolution Adhesion elongation Tg (mJ/cm2) during development (μιη) (bumping, peeling) (%) (°C) Example 1 - - - 61 202 14 Example 2 1000 50 with 65 201 15 Example 3 400 10 with 64 203 15 Example 4 350 8 with 61 220 15 Example 5 350 6 without 65 223 15 Example 6 300 6 without 62 220 16 Example 7 250 6 No 66 219 16 Example 8 350 6 No 65 225 14 Example 9 350 6 No 51 225 13 Example 10 300 6 No 59 221 10 Example 11 300 6 No 50 235 14 Example 12 300 4 No 85 226 17 Example 13 300 6 No 57 230 22 Example 14 250 6 No 52 220 15 Example 15 300 6 No 56 226 13 Example 16 200 6 No 58 222 16 Example 17 300 6 No 51 223 14 Comparison Example 1 750 15 No 60 218 15 Comparative Example 2 500 10 None 56 220 17 Comparative Example 3 800 12 No 60 225 16 Comparative Example 4 350 6 No 8 158 38 140879.doc -64· 201005002 [Table 3]

Damage rate (%) of copper discoloration film thickness after chemical hardening (cracks, pleats) Example 1 108 None - Example 2 108 No Example 3 107 No Example 4 100 No Example 5 101 No Example 6 100 No Example 7 100 No Example 8 102 No Example 9 102 No Example 10 101 No Example 11 100 No Example 12 100 No Example 13 102 No implementation Example 14 101 No Example 15 101 No Example 16 100 No Example 17 100 No Comparative Example 1 122 No Comparative Example 2 116 No Comparative Example 3 127 Serious No Comparative Example 4 135 Seriously No Example 1~ In the case of 17 at a low temperature hardening of 180 ° C, excellent chemical resistance can be achieved. At the same time, 140879.doc -65-201005002 exhibiting an elongation of 50% or more, high mechanical properties, and excellent heat resistance of 20 (Tg or more Tg, and low residual stress characteristics of 25 MPa or less) A polyimide resin having excellent low-temperature curing properties which have not been present so far and a photosensitive resin composition containing the same are provided. Further, in Examples 3 to 17, excellent photosensitive properties can be obtained, and further, in Example 4 In the case of ～17, excellent heat resistance was obtained, and in Examples 5 to 17, excellent adhesion during development was obtained, and in Examples 6 to 17, the discoloration of the copper surface after curing was suppressed. In Example 1, a polyamine resin in which a methyl methacrylate group is directly bonded to an amine group of AIPA and a radically polymerizable unsaturated bond group (AIPA_MA) is introduced as a raw material via a methacrylamide structure is used. However, since the degree of freedom of the unsaturated bonding group is low, the photosensitive property is remarkably inferior to the examples, and since the photocrosslinkability is low, the chemical resistance is also significantly inferior to the examples. In Comparative Examples 2 and 3, AIPA amine The copolymerization ratio of the radically polymerizable unsaturated binder group (for example, AIPA_MO) is lower than the preferred range of the present invention, but the photosensitive property is deteriorated due to the decrease of the radical polymerizable unsaturated binder group, and The structure from AIPA was reduced, so the chemical resistance was also significantly inferior to the examples. In Comparative Example 4, the resin film composed of the prior art photosensitive polyimide precursor composition was subjected to a temperature of 180 ° C. Low temperature hardening, but since the imidization is not complete, any of mechanical properties, heat resistance, residual stress, and chemical resistance is also significantly inferior to the examples. [Industrial Applicability] The photosensitive of the present invention Resin composition and polyamine resin used therein, 140879.doc -66 - 201005002 Suitable for use as an insulating material for electronic parts, a surface protective film for a semiconductor device, an interlayer insulating film, an α-ray shielding film, or the like A photosensitive resin composition used for forming a heat-resistant coating film in a semiconductor device including an image sensor, a micromachine, or a microactuator.

140879.doc •67·

Claims (1)

201005002 VII. Patent application scope: 1. A polyamido resin, which is in the range of 2~15〇, and the number of repeats reaches 8总数~1〇〇% of all structural units constituting the polyamide resin. The method within the range includes the structural unit shown in the following formula: • ·-(1) In the formula, X is a trivalent organic group having a carbon number of 6 to 15, and mgo or 2, Y is a divalent organic group having a carbon number of 6 to 35 when m=〇, and carbon when m=2. The tetravalent organic group 'R1' of 6 to 35 may contain an aliphatic group having at least one radical polymerizable unsaturated bonding group having an atom other than carbon and having a carbon number of 5 to 20. A polyamine resin having a structure represented by the following formula (2) in such a manner that the number of repetitions η in the following formula (2) is 8 % or more based on the total number of all the structural units constituting the polyamine resin: ] 140879.doc 201005002 is a divalent organic group having a carbon number of 6 to 35, a tetravalent organic group having a carbon number of 6 to 35 when m==2, and W is a divalent organic group having a carbon number of 6 to 15, and ! In the above integer, (η + k) is an integer of 5 to 150, and R1 may contain an aliphatic group having 5 to 2 carbon atoms having an atom other than carbon and having at least one radical polymerizable unsaturated bonding group. 3. A polyamine resin which has a structure represented by the following formula (3) as a structural unit, and the number of repetitions n in the above formula (3) is 8 to 100 in the total number of all structural units constituting the polyamide resin. Within the range of %, [Chemical 3] (wherein, X is a trivalent organic group having a carbon number of 6 to 15 'melon is ruthenium or 2, γ is a divalent organic group having a carbon number of 6 to 35 when m=〇, and a carbon number of 6 when m=2 a tetravalent organic group of ～35, W is a divalent organic group having a carbon number of 6 to 15, 1 is an anthracene or an integer of 1 or more, and (n+1) is an integer of 2 to 150, and R1 may contain an atom other than carbon, And a polyamine resin having a carbon number of 5 to 20, which has at least one radically polymerizable unsaturated bonding group, wherein the above-mentioned core is a formula (4) The base shown: [Chemical 4] 140879.doc 201005002 Ο Η A HR2 (4) where R2 is an aliphatic group having 4 to 19 carbon atoms having at least one radical polymerizable unsaturated bonding group} 5. The polyamine resin according to any one of claims 1 to 3, wherein the above & is a group having at least one (fluorenyl) acryloxymethyl group. 6. As claimed in claims 1 to 3. A polyamine resin wherein the above w, x and Y are each independently selected from the group consisting of an aromatic group, an alicyclic group, an aliphatic fluorenyl group, a decyloxy group, and the like. In the group 7. A photosensitive resin composition comprising: (A) 1 part by mass of the polyamide resin according to any one of claims 1 to 6, and (B) a photopolymerization initiator 〇 The photosensitive resin composition of claim 7 further comprising 100 parts by mass of the above (A) polyamine resin, and (c) having a light polymerization. The photosensitive resin composition according to claim 7 or 8, which further comprises 1 part by mass of 丨2 parts by mass based on 1 part by mass of the above (A) polyamine resin. (d) a thermally crosslinkable compound, wherein the (D) thermally crosslinkable compound is a compound which thermally crosslinks the above (A) polyamine resin or forms a compound having a heat crosslinked network structure. And a photosensitive resin composition according to claim 7, which further comprises the above-mentioned photosensitive resin composition. (A) Polyamine resin 1 part by mass (U~25 parts by mass (E) 12. The photosensitive resin composition according to claim 8, which further comprises (U) 25 parts by mass of (E) second smoulder with respect to 1 part by mass of the above (A) polyamine resin. The photosensitive resin composition of claim 9, which further comprises (E) a sulphur coupling agent in an amount of 0.1 part by mass to 100 parts by mass based on 100 parts by mass of the above (A) polyamine resin. The photosensitive resin composition according to claim 11, wherein the above (E) Shi Xi Xuan coupling agent is an organic ruthenium compound having a (monooxy)monomethane group or a (trisoxideoxy) group. 1. The photosensitive resin composition of claim 12, wherein the (E) sulphur coupling agent is an organic pulverized compound having (monooxyalkyl) anthracenyl or (tri-alkoxy) . The photosensitive resin composition of claim 13, wherein the above (E) Shi Xi Yuan coupling agent is a versatile compound having a (dialkoxy)monoalkylindenyl group or a (trialkoxy)indenyl group. 17. The photosensitive resin composition of claim 7, further comprising (F) a benzotriazine compound in an amount of 0.1 part by mass to 1 part by mass based on 100 parts by mass of the above (A) polyamine resin. . 18. The photosensitive resin composition according to the above item 8, which further comprises (F) a bismuth tris-based compound in an amount of 〇·1 to 1 part by mass based on 100 parts by mass of the above (A) polyamine resin. 140879.doc -4- 201005002 19. 20. 21. ♦ 22. 23. The photosensitive resin composition of claim 9, which further comprises (f) a stupid trisalt compound in an amount of from 1 to 1 part by mass based on 1 part by mass of the above (A) polyamine resin. The photosensitive resin composition of claim 11, which further comprises (F) a benzotriazine compound in an amount of 〇丨1 to 1 part by mass based on 1 part by mass of the (A) polyamine resin. A photosensitive resin composition solution containing the photosensitive resin composition according to any one of claims 7 to 2, and a solvent. A method of forming a hardened relief pattern, comprising: applying a photosensitive resin composition according to any one of claims 7 to 20 or a photosensitive resin composition solution of claim 21 to a substrate to form a step of coating a photosensitive resin composition; an exposure step of irradiating the coating film with active light directly or via a patterned mask; and a developing step of forming an embossed pattern by dissolving and removing the unexposed portion of the coating film by a developing solution And a step of heat-hardening the embossed pattern to form a hardened embossed pattern. A semiconductor device' having a hardened embossed pattern formed by a method of forming a hardened embossed pattern as claimed in claim 22. 140879.doc 201005002 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: Ο Ο Μ Η il II 1 ,,, V—N—Y Ν--· ·, (1) (〇H)m NH I Ri 140879.doc