TW200907567A - Photosensitive polyamic ester composition - Google Patents

Abstract

A photosensitive polyamic acid ester composition characterized by comprising 100 parts by mass of a polyamic acid ester consisting only of repeating units represented by a specific skeleton, 1-40 parts by mass of a photoinitiator, 30-1,500 parts by mass of a solvent, and 0-150 parts by mass of a polyamic acid ester consisting only of specific repeating units.

Description

[Technical Field] The present invention relates to a photosensitive polyphthalate composition which is used as a heat-resistant resin precursor for a surface protective film and an interlayer insulating film of a semiconductor device. It can be hardened at a low temperature, and can provide a hardened concave-convex pattern having high heat resistance and chemical resistance. Further, the present invention relates to a method for producing a heat-resistant cured concave-convex pattern using the photosensitive polyphthalate composition, a semiconductor device comprising the cured uneven pattern, and a method comprising the hardened concave-convex pattern t The layers are connected to each other and are provided with a laminate comprising titanium or a metal layer. [Prior Art] Polyimine resin has attracted attention as a material for microelectronics due to its high thermal stability and chemical stability, low dielectric constant, and excellent planarization ability. It is used as a material for a surface protection film or an interlayer insulating film of a semiconductor, or a multi-wafer module or the like. When a semiconductor device is fabricated using a polyimide resin, a polyimine resin film is usually formed on a substrate to produce a desired pattern by a photorefraction (丨ith. (4) phy) technique. Specifically, an indirect pattern forming method is employed in which a pattern of a photoresist is formed on a polyimide film by using a photoresist and a photomask, and then patterning of the polyimide resin is carried out by using (4). However, in this method, it is necessary to first form a photoresist pattern as a photomask on the polyimide film and then etch the polyimide film, and finally peel off the useless photoresist pattern. Further, 'the indirect pattern forming step' is low in resolution. Also, when using the button, you must use the toxic 130388.doc 200907567 substance as a solvent, so there are problems with safety. Human: Overcoming the problem as described above] The following method was put into practical use: introducing a photopolymerizable group of photopolymerization into a polyimine precursor, which directly forms a pattern of a polyimide film. For example, The following method or the like: First, a film is formed by using a photosensitive polyimide intermediate composition comprising: a compound having a double bond via a vinegar bond, an amine bond or an ion a polyimide or the like which is formed by binding a polyacrylamide to a polyacrylamide precursor, a photoinitiator, etc. Then, the exposed portion of the coating film is exposed by exposure to the film by a pattern of light. The imine precursor is insoluble to form a pattern, and then subjected to development treatment. Thereafter, heating is performed to remove the photosensitive group component, thereby converting the polyimine precursor into a heat-qualifying polyimine ( Refer to the non-patent literature. / / Xuan technology is generally referred to as photosensitive polyimide technology. With this technology, the problems associated with the above-mentioned process of using the non-photosensitive polyimide intermediate precursor can be overcome. hardening The formation of the convex pattern is increasing by the above-described photosensitive polyimide technology. Further, the semiconductor device (hereinafter also referred to as "element") is packaged on a printed circuit board by various methods depending on the purpose. Generally, by the wire bonding method in which the thin guide 7 is connected to the lead frame from the external terminal (the pad) of the 7L piece, the high speed of the pusher element and the operation frequency reach the GHZ. The difference in the length of the wiring between the components will affect the dynamic opening of the component. For the package of the component for the other end, the length of the package wiring must be correctly controlled, and the wire bonding cannot meet this requirement. Therefore, the following flip chip package is proposed. Forming a surface of the semiconductor wafer again I30388.doc 200907567 The wiring layer 'forms a bump (electrode) thereon, and flips the wafer directly onto the printed substrate. The chipping can control the wiring distance Therefore, it can be used for processing high-end components of high-speed signals, and because of its small package size, it can be used for mobile phones, etc., and its needs are rapidly expanding. In the case of using polyimine in the package, the polyimide layer is formed by a photoresist stripping step at a high temperature after pattern formation, a metal wiring layer such as Ab, and an etching step, and a solder electrode is formed (back). Therefore, the photosensitive polyimide resin used as the material of the rewiring layer must have excellent pattern formability and heat resistance, and must also have the photoresist used in each step described above. In recent years, due to the miniaturization and compositing of the device structure, the number of components that cannot be subjected to high-temperature processing has gradually increased. These components are packaged on the substrate. If a temperature of about 28 TC is applied, the yield will be significantly lowered. However, for the majority of photosensitive polyimides, in order to exhibit chemical resistance, it is necessary to make the temperature above 35 〇t. Harden under. Recently, however, there has also been proposed a photosensitive polyimide intermediate precursor composition which can be cured by low temperature. For example, Patent Document 1 proposes to heat-harden the following polyglycolate for 2 hours at 25 °C. a cured film comprising pyromellitic dianhydride and 4,4-oxydiphthalic dianhydride as a raw material of a tetracarboxylic acid, and using the meta-amine and the monoamine as a raw material of the amine However, when the "photosensitive polyimide" precursor composition is cured at a low temperature of 28 Å or less as shown in the comparative example described later, it is impossible to form a sufficient level of heat resistance and chemical resistance as a material of the rewiring layer. J30388.doc 200907567 [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 2-5-99353 [Non-Patent Document 1] Yamaoka. Table, "p〇ly file", 1990, pp. 27, No. 2, pp. 14-18 [Invention] [The problem to be solved by the invention] The object of the present invention is to provide a hardening at a low temperature of 28 CTC or less, and to provide both High heat resistance and chemical resistance hardening < The photopolymerizable polyacetate composition is a method for forming a cured polycondensate pattern of the photosensitive polyfluorene and the amine ester composition, and a semiconductor device comprising the cured concavo-convex pattern. [Technical means for solving the problem] In order to solve the above problems, the inventors of the present invention have found that by using a photosensitive polyphthalate composition containing a polyphthalate, a photoinitiator, and a solvent composed only of a specific repeating unit, it is possible to obtain a A photosensitive polyphthalate composition which is hardened at a low temperature and which provides a hardened concave-convex pattern having both high heat resistance and chemical resistance. The present invention has been developed based on the above-mentioned new findings. It is as follows. L. A photosensitive polyphthalate composition characterized by having a polyimido acid S曰 composed only of a repeating unit represented by the following general formula (1) with respect to a 100-mass fraction. (Α), containing 40 parts by mass of photoinitiator (Β), 3〇~15〇〇, amount of wound; gluten (c), and 〇~丨5〇 by mass of the following formula (2) Polyurethane composed of repeating units D). 130388.doc 200907567 [of π

(The quaternary aryl of one of the V double bonds can be used alone to make "+(10).9, r2 has a base, which can be the same or different. ~ Lower scent base, or fly with the following formula (4 ) It is not a tetravalent aromatic group, and it can be used in combination with two types. [Chemical 2] (3)

XX

[Chemical 3]

X2 is a tetravalent aromatic group which is not represented by the following formula (5) (4). Χτχχ γ and γ2 may be expressed by the following general formula (6). [化5] No

(5) Aromatic aromatic J, which can be phased

130388.doc (6) 10- 200907567 (A, B, n, D, E are hydrogen atoms or one of the carbon numbers 1~4 僧&# can be the same as the brother π valence of the aliphatic group, which is different from J.) ) [Chem. 6]

\\ 〇uy II I y LL II ii~0R3 ο ο (2) (R is a tetravalent aromatic group having a hydrogenated double bond Λ J. The soil x is expressed by the following formula (7) 7] "不Χ> γ γ3 is a divalent aromatic group represented by the following formula (8) (7) [Chemical Formula 8] > 2. The polyglycolate combination represented by the above (1) and Y2 a divalent aromatic group. The steroid group is represented by the following formula (9) or (10) [Chemical 9]

HiC 4 130388.doc (9) 200907567 [化 ίο]

The photosensitive polyamine amide composition according to any one of the above 1 to 2 wherein the photosensitive polyamine amide composition further contains 2 to 4 parts by mass of a crosslinking agent. 4. The photosensitive polyamidate composition according to the above 3, wherein the crosslinking agent is an alkoxymethylated melamine compound. 5. A method of forming a hardened concave-convex pattern, characterized by comprising: a coating step of forming a photosensitive polyamidite combination according to any one of the above 1 to 4 on a substrate in the form of a coating layer. Exposure step of exposing the coating layer by actinic rays through a photomask, or directly irradiating the coating layer with light, electron rays, or ion rays; developing step, using the developing solution to expose the exposed portion or the irradiation The portion is stripped and removed; and the heating step is performed to heat the obtained concavo-convex pattern. A semiconductor device comprising a hardened concave-convex pattern obtained by the method of forming according to the above 5. 7. A layered body comprising: a layer containing a hardened concave-convex pattern formed by curing the photosensitive polyamine amide composition according to any one of 1 to 4 above, and a layer A metal layer selected from at least one of the group consisting of titanium and (d). 8. A method for producing a laminated body, comprising: applying a photosensitive polyamido oxime composition according to any one of items 1 to 4 above to a substrate and drying the mixture; a step of forming a coating film on the substrate; and irradiating the coating film with ultraviolet rays by means of 130388.doc 200907567: removing the unpolished portion of the β coating film by using the material on/off to form a concave-convex pattern Heating the concave-convex pattern to form a step comprising: structuring the hardened surface layer by the polyimide resin, and using a layer selected from the group consisting of argon gas, oxygen gas, and tetra-carbonized carbon; a step of dry-engraving the surface of the layer by the gas; and a step of forming the metal layer of at least one selected from the group consisting of titanium and aluminum. [Effects of the Invention] According to the present invention, it is possible to provide a photosensitive polyamidate composition which can be cured at a temperature of 280 ° C or lower and which can provide a hardened concave-convex pattern having both high heat resistance and chemical resistance. And a laminate using the photosensitive polyacetal vinegar composition and a method for producing the same. [Embodiment] Hereinafter, embodiments of the present invention will be described in detail. <Photosensitive Polyurethane Composition> (A) Polyphthalate As the polyphthalate, a polyamine which is composed only of a repeating unit represented by the following formula (1) can be used. . [化11]

0 0

C*- - OfO

(1) 130388.doc •13- 200907567 (〇.3.m/(m + n)^〇9aR^^ base, which may be the same or different. χ1 '/, one of the olefinic double bonds The base group or the tetravalent aryl group represented by the following formula (3) may be used in combination with the above-mentioned four groups. 1 Bayer fragrant group, either alone (12) (3)

[Chem. 13]

X>XiC Y1 and γ2Α (5) The divalent aromatic group represented by the following formula (6) may be the same or different. [化15]

(6) The hydrazine is a hydrogen atom or a monovalent aliphatic group having 1 to 4 carbon atoms, which may be the same or different. )) In the case of the amine acid ester, the X1 group in the repeating unit is derived from the use as a raw material for the methyl dianhydride or the 3,3,4,4,-biphenyltetracarboxylic dianhydride, which may be 130388.doc - 14- 200907567 Two kinds of bisphthalic dianhydride can also be used in combination. The X2 base is derived from the 4,4'-gas used as a raw material.

In the synthesis of the polyglycolic acid barrier, a method in which a tetracarboxylic acid diester obtained by carrying out an esterification reaction of a tetracarboxylic dianhydride described later is directly supplied to a condensation reaction with a diamine can be preferably used. Among the above 4-brown acid vinegars, the γ1 and Υ2 groups of the pots are overflowing from the sulphate, and the γ1 and Υ2 groups are derived from the aromatic diamine used as a raw material. As an example of the aromatic amine of the aromatic group, it is exemplified by 1 4 phenylenediamine, 2-methyl-1,4-phenylenediamine, 25-methyl hydrazine 1/( ' ' 收 2,5_-methyl-l , 4-phenylenediamine, 2,3,5-tridecyl-1 4-phenylenediamine, 2 3 4 < TM Tian Gan, Ζ, 3,4,5-tetradecyl-1,4- Examples of the phenylenediamine include, for example, 14-phenylenediamine and 2,5-dimethyl 1,4-phenylenediamine. These may be used alone or in combination of two or more. The alcohol used in the vinegarization reaction of the above tetracarboxylic dianhydride is an alcohol having a dilute hydrocarbon double bond, and specific examples thereof include 2-methylpropenyloxyethanol and 2-propylpropaneoxyethyl #. 1-propenyloxy-2-propanol, 2-methylpropenylamine ethanol, 2-propenylaminoethanol, methylol ketone, 2-hydroxyethyl vinyl ketone, methacrylic acid 2 -hydroxyethyl ester, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxy-3-methoxypropyl acrylate, A 2-Hydroxy-3-decyloxypropyl acrylate, 2-hydroxy_3_butoxypropyl acrylate, 2-hydroxy-3-butoxy methacrylate Ester, 2-hydroxy-3-phenoxypropyl acrylate, 2-carbyl-3-phenoxypropyl methacrylate, 2-glycosyl 3-glycidylpropyl propylate , 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyl alkoxypropyl acrylate, 2-hydroxyl_3_cyclohexyloxypropane@曰, Acrylic acid 2-carbyl-3-cyclohexyloxypropyl phthalate, phthalic acid 2_甲130388.doc •15· 200907567 propylene methoxyethyl ester 2 hydroxypropyl ester, phthalic acid Formic acid 2_propyl methoxyethyl ester 2-hydroxypropyl ester, glycerin diacrylate, glycerin dimethacrylate, etc., but is not limited to such alcohols. These alcohols may be used alone or in combination 2 In the alcohol having an olefinic double bond, a part of methanol, ethanol, n-propanol, isopropanol, allyl alcohol, etc. may be used in combination, as described in JP-A-6-80776. f

I theoretically, the amount of the alcohol used in the esterification reaction of the tetracarboxylic acid dianhydride is equivalent to the U equivalent of the tetrasulphuric acid dianhydride (for example, refers to the addition of the tetracarboxylic dianhydride relative to the molar) 2 mol alcohols), in the present invention, if compared with 1.0 equivalent of tetraacid dianhydride, the G1~11()# amount of alcohol is made into four resorcinic diacetates', and finally the photosensitivity is obtained. The polyaminic acid I composition is preferred because it has improved storage stability. For the composition of the present invention, it is buried. The styrene ester (A) obtained by condensing the above specific tetracarboxylic acid diacetate with a specific diamine can be hardened at a low temperature of 280 ° C or lower, and can be taken as 楫J Heat resistance 'balance of chemical resistance and other properties. The tetrakis(di)di-diamine ear ratio used for the synthesis of poly-branched vinegar (4) is preferably about 1.0:1.0, and the eclipse according to the target polyglycolate (A) is at Η 0.7. Use within the range of ~...·3. Regarding the specific synthesis method of the polyglycolic acid used in the present invention, a previously known method can be employed. In this case, σ 万 万 日 ^ ^ ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° a method for producing a polyglycolate (A) by supplying the tetracarboxylic acid diester 130388.doc • 16 - 200907567 and a diamine to a condensation reaction; and by using four in the presence of an organic dehydrating agent A method in which a carboxylic acid diacetate and a diamine are supplied to a condensation reaction to produce a polyphthalate (A). Examples of the organic dehydrating agent include dicyclohexylcarbodiimide (DCC), diethylcarbodiimide, diisopropylcarbodiimide, ethylhexyl quinolamine, and diphenylcarbamate. Diimine, decyl dimethylaminopropyl propyl carbodiimide, 丨-cyclohexyl _3_(3-dimethylaminopropyl) carbodiimide hydrochloride, and the like. In the present invention, the m/(m+n) of the polyamido vinegar composed only of the repeating formula represented by the following general formula (1) is preferably (4) in the range of 〇·3 to 〇9, more preferably in the The range of 0·4~0.8. When m/(m+n) is 0 · 3 or more, it is resistant to chemical deduction! • The raw material is lifted back. When m/(m + n) is 09 or less, the resolution of the concave-convex pattern can be raised. The polyglycolate (A) used in this month has a weight average molecular weight of 疋 8000 〜 150,000, and more preferably 9 咖 ~ (9). When the weight average molecular weight is 8000 or more, 吋w 吋 mechanical properties are improved, and when the weight average molecular weight is 15,000 or less, the dispersibility in the aging solution is improved, and the unevenness is improved. (B) photoinitiator as a photoinitiator, indole formic acid, ... can be used: benzophenone, o-benzhydrylbenzene and di-diphenyl C-diphenyl ketone, Diphenylmethyl steel, ^ 〇τ bio; 2,2 丨-diethoxy acetophenone, and 2 fluorenyl-2-mercapto phenyl propyl ketone and the hydrazine derivative; 1-hydroxycyclohexyl Stupid ketone · thioxanthone, 2-mercaptopurine, no residue, isopropyl isopropyl ketone, and diethyl sneak 130388.doc 200907567 Yesterday (four), benzene, benzyl , _, and ... benzyl derivatives such as methoxy acetal 丨 Anliang private ... & U methyl ether and other benzoin derivatives ' 2,6-mono (4-diazidobenzylidene) _4 methyl Cyclohexene _, and ", two ... two stacks of benzylidene" cyclohexyl _ azide;} • stupid, one _ methoxy group) fat, phenyl propylene dione · 2 _ ( 〇 _ methoxy group -), _, 1_本基丙二明_2_(〇-ethoxymethyl), 1-phenylpropanedione_2_(1)-benzodiazepine m, !, 3_diphenylpropanetrifluoride_2_(〇_ethoxyoxy)

肟, 1-Benzyl-3. Ethoxypropyltris-_2_(〇·Benzamethylene sulfhydryl), Jiang et al; N-arylglycines such as N-phenylglycine; Benzoyl peroxide The above-mentioned hydrazines are preferred from the viewpoints of the curability and photosensitivity of the thick film, such as the peroxides; the aromatic (four) classes; and the ferrocenes. The addition of the photoinitiator 4 is preferably a diurethane mass fraction, more preferably 2 to 2 parts by mass, based on 1 part by mass of the polyamic acid vinegar (A). By adding with respect to 100 parts by mass of polyamine (A)! The photo-initiator of the above-mentioned parts is excellent in photosensitivity, and is excellent in thick film hardenability by adding 4 parts by mass or less of the photoinitiator. (C) Solvent As a solvent, it is preferred to use a polar organic solvent from the viewpoint of solubility of the polyphthalate (A) and the photoinitiator (B). Specific examples thereof include N,N-dimethylformamide, N-decylpyrrolidone (hereinafter also referred to as "NMP"), N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, and Ethyl alcohol monomethyl ether, cyclopentanone, γ-butyrolactone, α-ethinyl-γ-butyrolactone, tetramethylurea, 1,3_indolyl-2-flavor. Selenium _, Ν-cyclohexyl- 2-° thiophenone, etc. These may be used alone or in combination of two or more. 130388.doc -18- 200907567 According to the coating thickness, ψ m ^ degree, the hydrazine solvent can be used in the range of 100 parts by mass of the acidity. Preservation of the photosensitive polyamidate composition of the stability invention The organic solvent used as a solvent is preferably an alcohol. The alcohol which can be used is not particularly limited as long as it has an alcoholic base group = alcohol in the molecule, and as a specific example, it may be listed as an alcohol: n-propanol, isopropanol, n-butanol or the like. Butyl alcohol, the first ester of lactic acid esters such as ethyl ethoxide; propylene glycol _ 2 - methyl ether, propylene glycol" · diethyl ether C -% _ A) m. Propionate - 2 - diethyl ether, propylene glycol - 1 (n-propyl) Ether, propylene glycol 2_(n-propyl alcohol methyl ether, t @基) shouted propylene glycol early hospital kirai; acetaminophen, ethylene glycol ether, b- propyl ether special alcohol; 2-hydroxyl | Butyrate; ethylene glycol, C-*iso-%, propylene glycol. Among these, it is better to use lactic acid esters, propylene glycol mono p A u β, good basal scales, 2, basal isobutyric acid vinegars, and b (wheat), especially better to wear 7 疋 疋 疋 疋Ester, propylene glycol _ 丨 _ ethyl bond, propylene glycol small (n-propyl) scale. Alcohol_1_ does not have a olefinic double bond. 5 Θ 〇 - a good content in all solvents 疋 5 to 50% by weight, more preferably 1 〇 ~ ^ I / 〇. When the content of the alcohol having no olefinic hydrazine bond was 5% by weight and the ρ^ π system was double-coated, the storage stability of the photosensitive polyphthalate group was good. ° Further, § does not have a olefinic double bond content of 50% by weight or less of Japanese alcohol. In the case of S, the solubility of the polyaminic acid vinegar (4) becomes good (D) the polystyrene ester in addition to the main component of the present invention, that is, the polyamine phthalate (A) consisting only of the above formula ()) Representation of the repeating single, if necessary, to improve the composition of 130388.doc 200907567 can also be used without impairing the heat resistance and the poly-storage stability or the resolution of the concave-convex pattern represented by the following general formula (2), The glutamate (D) is optionally added within the range of chemical resistance. [Chemistry 16]

(2) X3 is expressed by the following formula (7)

(R3 is a tetravalent aromatic group having a valence group of an olefinic double bond. [7] Y is a divalent aromatic group represented by the following formula (8) [8] (8) Amidoxime 5 The amount of the hydrazine (D) to be added is preferably 150 parts by mass or less, more preferably H 00 parts by weight, based on 100 parts by mass of the polychar acid ester (Α). If the amount is 150 parts by mass. In the following, the heat resistance and the chemical resistance are not impaired. (Ε) The crosslinking agent is a crosslinking agent, and when the concave-convex pattern is heat-hardened, the main component of the present fx month can be added only by the above. The polyacrylic acid amide represented by the repeating unit represented by the general formula (]) can be crosslinked, or the crosslinking agent itself can form a crosslinked network. 1303SS.doc -20-200907567 The crosslinking agent can further enhance the heat resistance and Chemical resistance. As such a crosslinking agent, an amine resin or a derivative thereof can be preferably used, and among them, a urea resin, a diol urea resin, a hydroxyethylene urea resin, a melamine resin, a benzoic acid can be preferably used. Melamine resins, and derivatives thereof, particularly preferred are alkoxymethylated melamine compounds, examples of which can be listed Hexamethoxymethyl melamine. The amount of addition is preferably from 2 to 40 by mass with respect to 100 parts by mass of the polyglycolate (A) from the viewpoint of having properties other than heat resistance and chemical resistance. It is more preferably 5 to 3 parts by mass, and when it is added in an amount of two parts by mass or more, it exhibits desired heat resistance and chemical resistance, and when it is added in an amount of 40 parts by mass or less, it is stable in storage. (F) Other components may be arbitrarily added to enhance the photosensitivity, and as a sensitizer for improving photosensitivity, for example, rice ketone, 4,4, bis (diethylamine) may be mentioned. Diphenyl® I, 2'5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6 bis(4·-diethylaminobenzylidene) ring Hexanone, 2,6-bis(4,diethylaminobenzylidene)-4-methylcyclohexanone, 4,4,_bis(dimethylamino)chalcone, 4,4 , _ bis (diethylamino) chalcone, p-dimethylamino phenyl allenyl ketone, p-dimethylamino benzylidene ketone, 2 _ p-dimethylamino benzene Benzobenzil) benzoxazole, 2-(p-dimethylamino) Base-stretching vinyl)benzothiazole, 2-(p-dimethylaminophenyl-vinyl)isonaphthylthiazole, 1, Hongshuang (4, dimethylaminobenzylidene) acetone, M. double ( 4, · diethylaminobenzylidene) propionin, 3,3'_ shipyl_bis(7·diethylaminocoumarin), L-ethylidene-7-dimethylamino Coumarin, 3-ethoxylated 7-dimethylamine-based benzoin 3 benzyloxycarbonyl-7-dimethylamino coumarin, 3-methoxycarbonyl 130388.doc •21 · 200907567 -7-diethylamino coumarin, 3-ethoxycarbonyl _7-diethylamino coumarin, N-phenyl-Ν'-ethylethanolamine, N-phenyldiethanolamine , N_p-methyl-based monoethanolamine, N-phenylethanolamine, 4-morphinyl bicinchone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2 _ benzobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylamino) Styryl)benzothiazole, 2-(p-dimethylaminostyryl)naphthoquinone (1,2_d)thiazole, 2-(p-monomethylaminophenylhydrazino) phenylethylene , benzotricr, 5-methylbenzotriazole, 5-phenyltetrazole, and the like. Among these, from the viewpoint of photosensitivity, it is preferred to use a compound having a mercapto group in combination with a compound having a dialkylamino group. These may be used alone or in combination of 2 to 5 species. The sensitizer for increasing the photosensitivity is preferably used in an amount of 0.1 to 25 parts by mass based on 1 part by mass of the polyglycolate (A). In order to increase the resolution of the uneven pattern, a monomer having a photopolymerizable unsaturated bond may be arbitrarily added. As such a monomer, a (mercapto)acrylic compound which undergoes radical polymerization by a photopolymerization initiator is preferred, and is not particularly limited to the following: Ethylene glycol dimercapto acrylate as a representative of ethylene glycol or polyethylene glycol mono- or di-acrylate and methyl acrylate vinegar; propylene glycol or polypropylene glycol mono- or di-acrylate and methacrylate; glycerin Mono-, di- or tri-acrylate and mercapto acrylate; cyclohexane diacrylate and dimethacrylate; hydrazine, 4 - butanediol diacrylic acid vinegar and dimethacrylate; 1,6- Dipropylene acrylate and dimethyl acrylate acid; neopentyl glycol diacrylate and bismuth dimethacrylate, bisphenol A mono or diacrylate and methacrylate; benzene trimethacrylate Base 130388.doc •22- 200907567 Acrylate; isobornyl acrylate and isobornyl methacrylate; acrylamide and its derivatives; methacrylamide and its derivatives; trimethylolpropane triacrylate And methacrylic acid 3; glycerin or triacrylate vinegar and ACID day yl S 'di-, tri- or tetra-acrylate and aimed from pentaerythritol ester of methacrylic acid; and the compound of ethylene oxide or propylene oxide adducts of such compounds and the like. The monomer having a photopolymerizable unsaturated bond for improving the resolution of the uneven pattern is preferably used in an amount of parts based on 00 parts by mass of the polyglycolate (A). Further, a bonding aid for improving the adhesion to the substrate can be arbitrarily added. As the further auxiliary agent, γ-aminopropyl dimethoxydecane, Ν_(β-aminoethyl)-γ-aminopropylmethyldimethoxydecane, γ-glycidoxypropyl Methyldimethoxydecane, mercaptopropylmethyldimethoxydecane, 3-methylpropenyloxypropyldimethoxymethylnonane, 3-methylpropenyloxypropyltrimethoxy Base decane, dimethoxymethyl_3_piperidinylpropyl decane, diethoxy-3-glycidoxypropyl methyl decane, Ν_(3_: ethoxymethyl sulphur Butyldiamine, Ν_ [3 _(triethoxy oxalate) propyl] phthalic acid, benzophenone _3,3'-bis (Ν-[3-three Ethoxylated ethoxylate]propylamine]-4,4'-di-oroxic acid, benzo-anthracene, 4_bis(ν-[3-triethoxysulphonyl]propyl decylamine)-2 a decane coupling agent such as 5-dicarboxylic acid, 3-(triethoxydecyl)propyl succinic anhydride or hydrazine-phenylaminopropyltrimethoxy decane; and tris(ethylacetamethyleneacetate)aluminum, Aluminium tris(acetylpyruvate), ethyl acetoacetate, diisopropyl vinegar, etc. Among these, it is better to use the decane couple 130388.doc -23- 200907567 mixture. The amount of the auxiliary agent added is preferably in the range of 0.5 to 25 parts by mass based on 100 parts by mass of the polyphthalate (a). Further, in the photosensitive polyamine amide composition of the present invention, a thermal polymerization inhibitor may be optionally added in order to improve the stability of the viscosity or photosensitivity of the composition solution during storage. As a thermal polymerization inhibitor, hydroquinone, n_j'nitrodiphenylamine, p-tert-butyl catechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetrafene can be used. Acetic acid, i, 2_cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-t-butyl-p-methylbenzene, 5-nitroso-8-ylamino Porphyrin, 1-nitroso-2-naphthol, 2-nitroso-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso Phenylhydroxylamine ammonium salt, N-nitroso-N(l-naphthyl)hydroxylamine ammonium salt, and the like. The amount of the thermal polymerization inhibitor added to the photosensitive polyphthalate composition is preferably in the range of 5 to 12 parts by mass based on 1 part by mass of the polyphthalate (A). . In the photosensitive polyphthalate composition of the present invention, an organic titanium compound can be used arbitrarily as a component for improving heat resistance and chemical resistance. The organic titanium compound which can be used is not particularly limited as long as the organic chemical substance is bonded to the titanium atom via a covalent bond or an ion bond. In some cases, it is difficult to obtain a good pattern because the above-mentioned organotitanium compound interferes with the photoinitiator used in the present invention, and therefore an organotitanium compound which does not function as a photoinitiator is more preferable among the organotitanium compounds. . Specific examples of the organic titanium compound include trimethoxy(pentamethylcyclopentadienyl)titanium and the like. Further, examples of the organotitanium compound which can be used in the present invention include 130388.doc -24-200907567 titanium chelate compounds. Among the titanium chelate compounds, those having two or more alkoxy groups can obtain the stability of the composition and a good pattern, and therefore are preferable. As a specific preferred example, there are bis(triethanolamine) diisopropyl titanate, (double _24_glutaric acid) bis (n-butoxy) titanium, (bis-2,4-pentanedioic acid) titanium diisopropyloxide, bis(tetramethylpimelate) titanium diisotitanate, double (ethyl acetoacetic acid) diisopropyloxy and the like. Further, in the present invention, tetra (n-butoxy) titanium, tetra-titanium oxide, tetrakis(2-ethylhexoxide) titanium, tetraisobutyl oxide, titanium isopropoxide, tetra-titania, or tetra can also be used. Methoxypropane oxidized, tetramethyl benzene oxidized chin, tetra (n-indenyl oxidized) titanium, tetra (n-propoxy oxidized) titanium, tetrastearyl titanium oxide, tetra (bis 2,2-(allyloxymethyl) Butyl oxides such as tetradecyl oxides such as titanium (dioctylphosphoric acid) titanium isopropoxide, tris(dodecylbenzenesulfonic acid) titanium isopropoxide, etc., bis(glutaric acid) Titanium oxide such as titanium oxide, bis(tetramethylpimelate) titanium oxide or titanyl phthalocyanine, tetraethyl acetonide, such as titanium acetonate, and isopropyl tris(dodecylbenzenesulfonyl) a titanate coupling agent such as titanate or the like. The amount of the organic titanium compound to be added is preferably from 3 to 25 parts by mass, more preferably from 5 to 5 parts by weight, based on the (10) parts by mass of the polyphthalate (A). When the amount of addition is 〇3 parts by mass or more, the desired heat resistance and chemical resistance are exhibited, and when the amount is 25 parts by mass or less, the storage stability is excellent. In addition, the photosensitive polyamidate composition of the present invention may be appropriately formulated as needed, as long as the various characteristics of the photosensitive polyamidate composition of the present invention are not impaired. Scattering light absorber or film smoothing I30388.doc -25- 200907567

The various additives D tex represented by the property-imparting agent &; the hardened concave-convex pattern and the method for producing a semiconductor device> The use of the photosensitive polyphthalate composition to form a cured concave-convex pattern composed of a photosensitive polyimide resin The following aspects (a) to (d) are preferred. (a) a step of applying a photosensitive polyamine amide composition onto a substrate and drying it to form a coating film on the substrate.

(b) a step of irradiating the coating film with ultraviolet light via a patterned reticle or a main reticle. <(4) A step of forming a concave-convex pattern on the substrate by removing the unexposed Deng knife of the coating film by developing with a developing solution. (Step) A step of forming a hardened concave-convex pattern composed of a polyimide resin on the substrate by imidating = the valeric acid (tetra) in the concave-convex pattern by heat-hardening the concave-convex pattern. The base material which can be used for the method of forming the hardened concave-convex pattern includes m, metal, glass, semiconductor, metal oxide insulating film, nitride nitride, etc. It is preferable to use a tantalum wafer. The method of applying the photosensitive polyamidate composition to the soil used in the present invention may be a method of using a photosensitive polyamidate composition cloth cloth, for example, using a rotary type. Coater, stick coating,! A knife coating machine, a curtain coater, a screen printing machine, or the like is applied by a coating method, a spray coating method by a spray coater, or the like. The force = the method of drying the film ' can be air dried, using a tank or a crucible, and vacuum drying. Further, the drying of the coating film is preferably carried out under the conditions of not causing the imidization of the polyamidolate in the photosensitive polyamidolate composition, 130388.doc •26-200907567. Specifically, air drying or heat drying can be carried out at 20 C to 140 C for 1 minute to 1 hour. The coating film obtained as described above is exposed to light by an ultraviolet light source or the like through a mask having a pattern or a main mask using an exposure apparatus such as a contact exposure machine, a mirror projection exposure machine, or a stepper. After that, in order to improve the photosensitivity, etc., it is also possible to carry out exposure and post-exposure bake (PEB or pre-development (4) before any combination of any temperature and time as needed. The range of the conditions for the best roasting condition is 'the temperature is Qin 12 generation, time It is not limited to this range as long as it does not impair the characteristics of the photosensitive polyamidomate composition of the present invention. ==: The developer to be used, preferably poly-aracine The good solution of vinegar is the combination of the good solvent and the poor solvent. As a good solvent, it is preferably chloropyrrolidone, N. cyclohexyl-2-pyrrolidine, guanidine, cyclohexanone, γ-butane vinegar, "醯: monomethyl b, etc., as 坌, 々^ _ acetyl γ-butyrolactone propanol, sih h, methanol, ethanol, iso-solvent and lean, sputum, scorpion and leeches. The use of good relative to Bu Cai, the cold solution of the makeup heart and adjust the lean solvent. "4 ratio. In addition, you can also combine several solvents to make the method used for development, can be customized 1 method, for example旌 斤 知 know the development of the photoresist, etc.: Select and use any method. Ultrasonic treatment of the impregnation method In order to adjust the shape of the concave-convex pattern, etc., it is also possible to carry out post-development baking of any combination of temperature and time as needed, 130388.doc •27-200907567. For the pattern of the poly-waking acid vinegar obtained in the above manner, By teaching, the photosensitive component is volatilized and imidized, thereby converting into a hardened concave-convex pattern composed of a polyimide resin. As a method of heat hardening, a method using a hot plate, a method using an oven, and utilization can be selected. Various methods such as a method of temperature-programmed temperature-increasing oven can be set. Heating can be carried out at 150 ° to 280 °, 30 minutes to 5 hours.

The ambient gas during heat hardening may be either air or an inert gas such as nitrogen or argon. In the semiconductor device of the present invention, the hardened concave-convex pattern of the present invention can be used as a surface protective mi insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a protective film for a device having a bump structure, and is known. The manufacturing method of the semiconductor device is manufactured in combination. Further, the positive photosensitive resin composition of the present invention can also be used for applications such as interlayer insulation of a multilayer circuit, a protective layer of a flexible copper plate, a solder resist film, or a liquid crystal alignment film. <Manufacturing Method of Laminates> One aspect of a method of producing a laminate having a cured uneven pattern layer composed of a polyimide resin and a metal layer using the photosensitive polyimide composition described above The best is the following steps. After the step of forming the hardened concavo-convex pattern on the substrate by the method of forming the cured concavo-convex pattern, the surface of the hardened concavo-convex pattern layer is subjected to dry etching such as ashing or plasma etching. The dry etching treatment is preferably carried out using oxygen, argon, carbon tetrafluoride, etc. under the conditions of a pressure of 1 to 100 Pa and a time of 30 minutes. The surface of the hardened concave-convex pattern composed of the polyimide resin obtained on the substrate in the above manner is in contact with the surface, and a metal layer for bump or rewiring is further provided by a film forming method such as sputtering (titanium, aluminum Or a metal layer such as copper)" Thereby, the laminate of the present invention can be produced. Further, by combining the method for producing a laminate and the method for producing a known semiconductor device, it is possible to produce a metal layer having at least one selected from the group consisting of titanium and aluminum on the polyimide layer. Semiconductor device. <Examples Hereinafter, the present invention will be specifically described based on examples and comparative examples. In the examples, comparative examples and reference examples, the physical properties of the photosensitive polyamidate composition synthesized by the method described later were measured and evaluated according to the following method. (1) Weight average molecular weight The weight average molecular weight (Mw) of each polyamine ester synthesized by the method described later is measured by gel permeation chromatography (hereinafter also referred to as "Gpc") (standard polystyrene conversion). ). The analysis conditions of GPC are described below. Pillar · Showa Denko Co., Ltd. manufactures the trade name sho heart ft〇dex 805/804/803

Bath chaotropic solution: N-methyl. Comparison 〇 4〇 °C Flow rate. 1,0 ml/min Detector: Showa Denko Manufacturing Trade name 130388.doc •29· 200907567 (2) Determination of glass transition temperature (Tg) of polyimine coating On a 5 inch wafer (manufactured by Fujimi Electronics Co., Ltd., Japan) having a thickness of 625 ± 25 μm as a substrate, the film thickness after hardening is about 10 μm, which is synthesized by the method described later. The photosensitive polyamine amide composition was heated at 250 ° C for 2 hours under a nitrogen atmosphere to obtain a thermosetting polyimide film. The polyimine tape obtained by peeling off the obtained ceramsite wafer is made into a polyimide film.

The obtained polyimine belt was obtained by a thermomechanical test apparatus (tMA_50 manufactured by Shimadzu Corporation) in a range of 2 〇 to 5 Torr (TC range) with a load of 200 g/mm 2 and a temperature increase rate of l 〇 ° C/min. The measurement is carried out as the Tg 〇(3) hardened concave-convex pattern by using the tangential intersection of the thermal undulation point of the polyimine band in the measurement chart with the temperature on the horizontal axis and the displacement as the vertical axis, which is prepared by the method described later. The photosensitive polyamine amide composition was spin-coated on a 5 Å wafer and dried to form a film having a thickness of 1 〇 0111. Using a photomask with a test pattern, 'aligned with a parallel ray mask Exposure machine PLA-

Rinsing to obtain a concave and convex pattern

130388.doc -30- 200907567 J-time heat treatment 'This is to obtain a hardened concave-convex pattern composed of polyimine resin with a thickness of about (4) on the Shi Xi wafer. (4) Chemical resistance of the hardened concave-convex pattern The evaluation will be performed on the hardened concave-convex pattern obtained in the production of the hardened concave-convex pattern; potassium hydroxide (hereinafter also referred to as "K0H") / dimethyl sulfoxide (hereinafter also referred to as "deleted") / 3_A The weight ratio of oxy_3_methylbutanol is i: 5 9 ♦ 4 0 in the mixture of 〇〇. Factory τ 'win, Lord! After observing the next stain for 1 hour at 1 00 C, observe the surface pattern. Observe the surface pattern after 4 () minutes of immersion in the mixed solution of "TMah" V dimethyl zephyr (hereinafter referred to as "TMah" V dimethyl nitrous oxide in 4 · 96 cycles). When observing, if there is no pattern expansion and dissolution, peeling of the pattern, or crack of the coating film, it is considered to be acceptable. (5) Evaluation of the reflow resistance of the hardened concave-convex pattern for the above (3) The hardened concave-convex pattern obtained in the production of the hardened concave-convex pattern is described by the method described in the evaluation of the chemical resistance of the (4) hardened concave-convex pattern, and potassium hydroxide/dimethyl sulfoxide (DMS〇)/3 A mixture of _methoxy-3-methylbutanol is treated, and then a flux is applied to the pattern (trade name 〇〇lb〇nd, trade name R5〇〇3, manufactured by Alpha Metals japan) (per minute 500 rpm, spin coating for 2 sec.), and heated to a peak temperature under a nitrogen atmosphere using a simulated reflow condition of a mesh belt continuous firing furnace (manufactured by Koyo Thermo System, model number 6841_20AMC-36) 260 C. The so-called analog reflow conditions refer to the evaluation of semiconductor devices. The method is related to the standard specifications of the US semiconductor industry group, namely, the reflow soldering conditions described in item 7.6 of IPC/JEDEC J-STD-020A. The melting point of the solder is assumed to be 22 〇〇c, and the specification is 130388. .doc 31 200907567. The cured film treated under the above-mentioned simulated reflow conditions is immersed in a flux cleaning agent (Pen Alpha, manufactured by Arakawa Chemical Co., Ltd., trade name ST·100SX) for 1 hour. After the flux was removed and dried, the surface pattern was observed under an optical microscope. If there was no swelling or dissolution of the pattern, peeling of the pattern, or crack of the coating film, it was judged to be acceptable. Reference Example 1 > Synthesis of acid ester 1) 43.6 g of pyromellitic dianhydride (pmda) as tetrahedic acid and 62.0 g of 4,4'-oxydiphthalic dianhydride (〇DPA) were placed in a capacity of In a 2 liter separable flask, add 106·2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone, and stir at room temperature, and add 81·5 while stirring. The reaction mixture is obtained by pyridine of g. After the exotherm caused by the reaction is completed After cooling to room temperature, it was allowed to stand for 16 hours. Then, while cooling in an ice bath, a solution of 165.1 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added. It took 40 minutes to add to the reaction mixture, and then, while stirring, a suspension of 39.3 g of 1,4-phenylenediamine as a diamine suspended in 350 ml of γ-butyrolactone was added for 60 minutes. In the above reaction mixture. After further mixing for 2 hours at room temperature, 30 ml of ethanol was added and stirred for 1 hour, followed by the addition of 400 ml of γ-butyrolactone. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid. The obtained reaction liquid was added to 3 liters of ethanol to form a precipitate composed of a crude polymer. The resulting crude polymer was separated by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained polymer solution of 130388.doc -32-200907567 was added dropwise to 28 liters of water to precipitate a polymer, and the obtained precipitate was separated by filtration, and dried under vacuum at 4 Torr for 48 hours to obtain a powder. Polymer (polyamidomate). The weight average molecular weight (Mw) was measured by gel permeation chromatography (standard polystyrene conversion), and it was 16,000 Å < Reference Example 2 > (Synthesis of Polyurethane 2) Using 58.8 g of 3, 3',4,4'-biphenyltetraphthalic acid dianhydride (BpDA) and a 4,4'-oxydiphthalic dianhydride (〇DpA) as a tetracarboxylic acid, using 39 3 $ As the diamine, 1,4-phenylenediamine was reacted by the method described in the above Reference Example to obtain a polyphthalate 2. The weight average molecular weight (Mw) was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, it was obtained. <Reference Example 3> (Synthesis of Polyurethane 3) 47.1 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BpDA) and 74 5 Lu 4,4·-oxygen were used. Bis, adipic acid dianhydride (〇DPA) is used as the tetracarboxylic acid, and 1,4-phenylenediamine is used as the diamine, and the polyamine is obtained by the method described in the above Reference Example. Acid ester 3. The weight average molecular weight (Mw) was measured by gel permeation chromatography (standard polystyrene conversion) and found to be 17 Å. This <Reference Example 4 > (Synthesis of Polyurethane 4) Using 94.2 g of 3,3,4,4,4-biphenyltetracarboxylic dianhydride (BpDA) and 24 8 g of 4,4' - Oxygen bis-phthalic acid dianhydride (〇DpA) as a tetracarboxylic acid, using 1,4-thindiamine as a diamine in the above-mentioned reference example w Amino acid vinegar 4. The weight average molecular weight (Mw) was determined by the gel permeation chromatography (standard polystyrene conversion), and the result was i6 〇〇〇. a <Reference Example 5 > (Synthesis of Polyurethane 5) 130388.doc -33- 200907567 Using 21.8 g of pyromellitic dianhydride (PMDA), 29.4 g of 3,3',4 , 4'-biphenyltetracarboxylic dianhydride (8 卩〇 human) and 62.0 § 4,4, oxydiphthalic dianhydride (ODPA) as tetracarboxylic acid, using 39.3 g of l,4-benzene The diamine was reacted as a diamine by the method described in Reference Example 1 above to obtain a polyamine 5 . The weight average molecular weight (Mw) was measured by gel permeation chromatography (standard polystyrene conversion) and found to be 1 8000. <Reference Example 6 > (Synthesis of Polyamine 6) Using 58.8 § 3,3',4,4'-biphenyltetracarboxylic dianhydride (8-8) and 62. , 4'-oxybis-p-dibenzoic acid dianhydride (〇DPA) as a tetracarboxylic acid, using 49 4 • Ο 2,5-dimethyl-1,4-phenylenediamine as the diamine, using the above reference examples The method described in 1 is reacted to obtain polyphthalate 6. The weight average molecular weight was measured by gel permeation chromatography (standard polystyrene conversion) and the result was 18,000. <Reference Example 7> (Synthesis of Polyurethane 7) 87.2 g of pyromellitic dianhydride (pMDA) was used as the tetracarboxylic acid, and 39.3 g of 1,4-phenylenediamine was used as the diamine. The method described in the above Reference Example was allowed to react to obtain a polyphthalate 7. However, the obtained poly-character is insoluble in the solvent. The weight average molecular weight (Mw) cannot be determined. <Reference Example 8 > (Synthesis of Polyurethane 8) 117.7 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was used as the acid, and 39.3 was used as the 4. The amine is used as a diamine, and the user is allowed to react to obtain a polyphthalate 8 by the method described in the above. The weight average molecular weight was measured by gel, moxibustion, chromatography (standard polystyrene conversion) (the permeation was 1 'knot 130388.doc -34- 200907567 <Reference Example 9> (polyamide 9 Synthesis) using 23.5 g of 3,3,,4,4,-biphenyltetracarboxylic dianhydride (BpDA) & 99.3 § 4,4'-oxydiphthalic dianhydride (〇DPA) as Tetracarboxylic acid, using π"^ ι,4 phenylenediamine as a diamine, which is reacted by the method described in the above Reference Examples to obtain a polyphthalate 9. Using gel permeation chromatography (standard polyphenylene) In terms of ethylene, the weight average molecular weight (Mw) was measured and found to be 17 Å. <Reference Example 10> (Synthesis of polyglycolate 1 使用) Using 58.8 g of 3, 3, 4, 4, - Pyromellitic dianhydride (BpDA) & 62 〇§ 4,4'-oxydiphthalic dianhydride (〇DPA) as tetracarboxylic acid, using 54 6 g of 2,4,6-didecyl -1,3-phenylamine as a diamine, which was reacted by the method described in the above Reference Example} to obtain a polyphthalate ester. The weight was measured by gel permeation chromatography (standard polystyrene conversion). Average molecular weight (Mw), knot 18000. <Reference Example 11 > (Synthesis of Polyurethane 11) Using 124.1 g of 4,4·-oxydiphthalic dianhydride (〇DpA) as a tetracarboxylic acid, using 72·8 g 4,4,-diaminodiphenyl ether as a diamine, which was reacted by the method described in the above Reference Example 1 to obtain a polyphthalate U. Using gel permeation chromatography (standard polyphenylene) The weight average molecular weight (Mw) was measured in terms of ethylene and found to be 21,000. <Reference Example 12> (Synthesis of Polyurethane 12) 58.8 g of 3,3',4,4'-biphenyltetracarboxylic acid was used. Anhydride (Bpda) and 62.0 g-oxo-di-n-dicarboxylic acid two-needle (DPA) as tetra-rebel, using 27.5 g of 1,4-phenylamine and 11.8 g of iotatriene The diamine was reacted to obtain a polyamidate oxime 2 by the method described in the above Reference Example 1. The weight average was measured by gel permeation chromatography (standard polystyrene conversion) using condensate 130388.doc -35 - 200907567 Molecular weight (Mw), the result was 16,000. <Example 1> Using the obtained polyphthalate 1, the saltiness was prepared by the following method. The polyglycolate composition was prepared. The composition was evaluated. i 〇〇g of poly phthalate 1 and 4 g of 1,3-diphenyl glycerol 2 - (anthracene ethoxycarbonyl) hydrazine (photoinitiator), 4 g of tetraethylene glycol dimethacrylate, 2 phenyl 1-phenyl-5-mercaptotetrazole, 8 g of hexamethoxymethyl melamine, 4 莒 N-phenyldiethanolamine, 3 § Ice [3. (triethoxydecyl)propyl] phthalic acid, and 0.02 g of 2-nitroso-hydrazine, naphthol are dissolved together in 80 g of NMP and 20 g In a mixed solvent of ethyl lactate. The photosensitive polyamine amide composition was prepared by further adding a small amount of the mixed solvent to adjust the viscosity of the obtained solution to about 3 Torr. The Tg of the polyimide film obtained from the composition was 290 °C. Further, in the chemical resistance test conducted by KOH/DMSO/3-decyloxy_3_mercaptobutanol, no dissolution of the pattern and peeling of the pattern were observed. In the chemical resistance test of TMAH/DMSO, no swelling or dissolution of the pattern, peeling of the pattern, or cracking of the coating film were observed. In the anti-reflow process test of the hardened concave-convex pattern which was subsequently carried out, the dissolution of the pattern, the peeling of the pattern, and the crack of the coating film were not observed. <Example 2> A photosensitive polyamine amide composition was prepared in the same manner as in Example 1 except that poly phthalate 2 was used instead of poly phthalate oxime. The 130 μg of the polyimide film obtained from the composition has a Tg of 270 ° C. Further, in the chemical resistance test by KOH/DMSO/3-decyloxy-3-methylbutanol, no dissolution of the pattern, peeling of the pattern, and cracking of the coating film were observed. In the chemical resistance test of TMAH/DMSO, the swelling and dissolution of the pattern, the peeling of the pattern, and the crack of the coating film were not observed. In the anti-reflow process test of the hardened concave-convex pattern which was subsequently carried out, no dissolution of the pattern, peeling of the pattern, or cracking of the coating film were observed. <Example 3 >

A photosensitive polyamidate composition was prepared and evaluated in the same manner as in Example 1 except that polyphthalate 3 was used instead of polyphthalate 1. The polyimine coating film obtained from the composition had a Tg of 268. (: Further, in the chemical resistance test by KOH/DMSO/3-methoxy-3-methylbutanol, no dissolution of the pattern, peeling of the pattern, or crack of the coating film was observed. In the chemical resistance test of TMAH/DMSO, no cracking and dissolution of the pattern, peeling of the pattern, and cracking of the coating were observed, and in the anti-reflow process test of the hardened concave-convex pattern which was subsequently performed, The dissolution of the pattern, the peeling of the pattern, and the crack of the coating film were not observed. <Example 4> In the same manner as in Example 1, except that polyphthalate 4 was used instead of the polyphthalate oxime A photosensitive polyamido vinegar composition was prepared and evaluated. The Tg of the polyimide film obtained from the composition was 280 t. Further, using KOH/DMSO/3-methazine, 3 fields* τλ - Chemical resistance by T-milyl-3-methylbutanol I30388.doc -37- 200907567 In the pharmaceutical test, no dissolution of the pattern, peeling of the pattern, cracking of the coating film, and resistance to TMAH/DMSO were observed. In the chemical test, no swelling or dissolution of the pattern, peeling of the pattern, or coating of the film was observed. In the anti-reflux process test of the hardened concave-convex pattern which was carried out thereafter, no dissolution of the pattern, peeling of the pattern, or crack of the coating film were observed. [Example 5 &gt; In addition to the use of poly-proline A photosensitive polyphthalate composition was prepared and priced in the same manner as in Example Ο 1 except that the ester 5 was used in place of the polyamidoxime. The polyimide film obtained from the composition was used. It is 28 。. Further, in the chemical resistance test by KOH/DMSO/3-methoxy-3-methylol, no dissolution of the pattern, peeling of the pattern, and coating were observed. Crack. In the chemical resistance test of TMAH/DMSO, no swelling or dissolution of the pattern, peeling of the pattern, crack of the coating film, and resistance to reflow process test of the hardened concave-convex pattern performed thereafter. No dissolution of the pattern, peeling of the pattern, or crack of the coating film was observed in the middle. <Example 6 &gt; The same procedure as in Example 1 was carried out except that the polyphthalate 6 was used instead of the polyphthalate oxime The photosensitive polyphthalate composition was prepared and evaluated. The polyimine coating film obtained from the composition was 28 〇. = In the chemical resistance test conducted by K〇H/DMSO/3_methoxy-3-methylbutanol No dissolution of the pattern was observed, and the crack of the coating was observed. The chemical resistance test of TMAH/DMSO was also not observed. 130388.doc -38· 200907567 The swelling and dissolution of the pattern were observed. The peeling of the pattern and the crack of the coating film were not observed in the anti-reflow process test of the hardened concave-convex pattern which was carried out thereafter, and the dissolution of the pattern, the peeling of the pattern, and the crack of the coating film were not observed. &lt;Example 7&gt; A photosensitive polyphthalate composition was prepared in the same manner as in Example 2, except that polyphthalate 11 was used instead of 5% by mass of polyphthalate 2, And evaluate. The polyimine coating film obtained from the composition was 255 (). Further, the chemical resistance test was carried out using KOH/DMSO/3-decyloxy-3-3 mercaptobutanol. No dissolution of the pattern, peeling of the pattern, or cracking of the coating film were observed. In the chemical resistance test of TMAH/DMSO, no swelling or dissolution of the pattern, peeling of the pattern, or cracking of the coating film were observed. In the anti-reflow process test of the hardened concave-convex pattern which was subsequently carried out, no dissolution of the pattern, peeling of the pattern, or crack of the coating film was observed. [Comparative Example 1 &gt; A photosensitive polyphthalate composition was prepared and evaluated in the same manner as in the Example except that polyacetamide was used. However, the composition was residual polymerization in Φ && % A , The insoluble component of the substance could not be uniformly applied to the SB circle. 'The desired concave-convex pattern could not be obtained. <Comparative Example 2 &gt; In addition to the use of polyamide, the + S-day 8 was substituted for the polyamidate 1 In addition, in the same manner as in Example 1, the preparation of the photosensitive polyamidate composition was carried out. Evaluation: 130388.doc -39· 200907567 The Tg of the polyimide obtained from the composition was 29 (Tc. In the chemical resistance test of TMAH/DMSO, no swelling or dissolution of the pattern was observed, Peeling of the pattern, crack of the coating film. However, in the chemical resistance test by KOH/DMSO/3-methoxy-3-mercaptobutanol, the pattern was found to be dissolved. In the anti-reflow process test of the hardened concave-convex pattern, cracks were also observed on the coating film. <Comparative Example 3 &gt; In addition to using polyphthalate 9 instead of polyphthalate 1, The photosensitive polyamine amide composition was prepared and evaluated in the same manner as in Example 1. The Tg of the polyimide film obtained from the composition was 255 ° C. Chemical resistance to TMAH/DMSO In the test, no swelling/squeezing and dissolution of the pattern, peeling of the pattern, and cracking of the coating film were observed. However, the chemical resistance with KOH/DMSO/3-methoxy-3-methylbutanol was observed. In the test, it was found that the pattern was dissolved. The anti-reflow process test of the hardened concave-convex pattern was carried out thereafter. 'Cracks were also observed on the coating film. <Comparative Example 4 &gt; Photosensitive polyamine was prepared in the same manner as in Example 1 except that polyphthalate 1 was used instead of polyphthalate 1. The acid ester composition was evaluated and evaluated. The Tg of the polyimide film obtained from the composition was 260 ° C. However, using KOH / DMSO / 3-methoxy-3-methylbutanol In the chemical resistance test conducted by the chemical resistance test conducted by TMAH/DMSO, the pattern dissolution was found. In the subsequent test of the resistance to reflow process of the hardened concave and convex 130388.doc 200907567 pattern, Cracks were also observed on the film. &lt;Comparative Example 5 &gt; A photosensitive polyamidate composition was prepared in the same manner as in the case of Example 2 except that polylactomic acid was used instead of 75% by mass of polyphthalate 2 And evaluate. The polyimine coating film obtained from the composition had a Tg of 230. (:. However, the chemical resistance test using KQH/DMSQ/3-methoxy_3_mercaptobutanol, using TMah/dms

The test was found to have dissolved. Cracks were also observed on the film during the hard reflow process test of the hard::: pattern. &lt;Comparative Example 6&gt; When the photosensitive polyacetate composition obtained in Comparative Example 2 was evaluated, the conditions for curing the uneven pattern were changed to heat treatment at 200 C for 1 hour under a nitrogen atmosphere, and then In the discussion. The heat treatment was carried out for 2 hours under c, and the hardened bumps composed of polyamidene resin with a thickness of about 6.0 μm τ were obtained on the dream wafer. Fortunately, 眚姑#儿组# „固茶Λ Chemical resistance test and anti-return test. &amp; The Tg of the polyimide film obtained from the composition is (10). In the chemical resistance test of TMAH/D_, it was not observed. To the face of Tuzai, moisturizing and dissolving, stripping of the pattern, coating / main skin and teaching. However, Yuli KOH/DMSO/3-methoxy_3_methyl is chemically resistant to butanol. In the drug-based test, the pattern was found to be dissolved. In the anti-reflow process test of the hardened concave and convex relief pattern, the crack was also observed in the coating film. ~ whip 130388.doc 200907567 &lt;Comparative Example 7 &gt; A photosensitive polyamine amide composition was prepared and evaluated in the same manner as in Example 1 except that poly phthalate 12 was used instead of poly phthalate 1. From the composition The Tg of the obtained polyimide film was 270 ° C. In the chemical test using TMAH/DMSO No swelling or dissolution of the pattern, peeling of the pattern, or cracking of the coating film were observed. However, in the chemical resistance test using KOH/DMSO/3-methoxy-3-methylbutanol, the pattern was found. Dissolution. In the anti-reflow process test of the hardened concave-convex pattern which was carried out thereafter, cracks were also observed on the coating film. [Industrial Applicability] The photosensitive t-proline acid composition of the present invention It can be preferably used in the field of producing photosensitive materials useful in electrical and electronic materials such as semiconductor devices and multilayer wiring boards. More specifically, the composition of the present invention can be preferably used as a hardening agent at low temperatures. Further, it is possible to provide a photosensitive polyamic acid vinegar composition having a high heat resistance and a chemically hardened concave-convex pattern. 130388.doc 42·

Claims (1)

200907567 I. 申 谤 谤 : : : 感光 感光 感光 感光 感光 感光 感光 感光 A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A 40 parts by mass of the photoinitiator (b), 500 parts by mass of the solvent (〇, and 〇 15 parts by mass of the polyfluorene consisting only of the repeating unit represented by the following formula (2)) Amino acid c or. — c V (〇.3$m/(m+n) each 〇9;... and the valence group, which may be the same or different; χΙ = = a dilute smoky double bond - an aromatic group, or represented by the following formula (4) ::3) Indicates that the four-price single use can also be used in combination; two kinds of Jia Fangxiang base, can be single [2] (3) XX [Chemical 3] X2 is a tetravalent aromatic group represented by the following formula (5); 130388.doc (5) 200907567 γ and Y are divalent aromatic groups represented by the following general formula (6), which may be the same or different; [Chemical 5] (6) Can be the same or different)) [Chemistry 6] (R3 is a valent group having a dilute hydrocarbon double bond; and X3 is a tetravalent aromatic group represented by the following formula; [Chem. 7] (7) Y3 is a divalent aromatic group represented by the following formula (8)) [Chem. 8] (8). 2. The photosensitive polyamido vinegar composition according to item 1, wherein the divalent aromatic group represented by γ 1 and γ is a divalent aromatic compound represented by the following formula (9) or (1〇) Base, 130388.doc (9) 200907567 [Chem. 9] [化10] (10) The photosensitive polyamidate composition according to any one of claims 1 to 2, wherein the photosensitive polyamido acid S composition further contains 2 to 40 parts by mass of a crosslinking agent . 4. The photosensitive polyphthalate composition of claim 3, wherein the crosslinking agent is an alkoxymethylated melamine compound. A method for forming a hardened concave-convex pattern, comprising: a coating step of forming a sensation "S-poly lysine vinegar composition" on a substrate in a form of a coating layer as claimed in any one of claims The exposing step of exposing the coating layer to the coating layer by means of actinic rays, or directly irradiating the coating layer with light, electron rays, or ion rays; developing step, using the developing solution to expose the exposed portion or the The irradiation portion is eluted and removed; and the heating is performed. Step ' is to heat the obtained concave-convex pattern. A semiconductor device, which is injurious to the wearer - has a hardened concave-convex pattern which is obtained by the method of forming the claim 5. a layered body, the material of which has a layer comprising a hardened concave pattern formed by hardening a photosensitive polyamidamine composition as claimed in any one of claims 1 to 4, and A metal layer selected from the group consisting of at least one of 130388.doc 200907567 consisting of titanium and aluminum. A method for producing a laminate, comprising: applying a photosensitive polyphthalate composition according to any one of claims 1 to 4 to a substrate and drying, thereby drying the substrate a step of forming a coating film; a step of irradiating the coating film with ultraviolet rays through a mask having a pattern; or developing with a developing solution; thereby removing the unexposed portion of the coating film to form on the substrate a step of forming a concave-convex pattern: a step of forming a layer comprising a fluorinated::pattern composed of a polyimide resin on the substrate by heating the concave-convex pattern 2; using a selected from the group consisting of argon, oxygen, and tetragon At least one of the gases - the surface of the layer is dry-touched to the group:: a step of contacting the layer to form a metal layer selected from the group consisting of titanium and metal. 130388.doc 200907567 VII. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 8. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: 1 130388.doc