TW201041935A - Polyimide-based polymers, copolymers thereof and positive type photoresist compositions comprising the same - Google Patents

Abstract

Polyimide-based polymers and copolymers thereof are provided. Further provided is a positive type photoresist composition comprising at least one of the polyimide-based polymers and copolymers thereof as a binder resin. The photoresist composition exhibits high resolution, high sensitivity, excellent film characteristics and improved mechanical properties, which are required for the formation of semiconductor buffer coatings.

Description

201041935 VI. Description of the Invention: [Technical Field] The present invention relates to a polyamidamide-based polymer comprising a dianhydride group having a specific structure of a repeating unit, and/or the poly A copolymer of a melamine-based polymer. The present invention also relates to a positive photoresist composition comprising at least one polyamidamide-based polymer and/or a copolymer thereof as an adhesive resin for achieving high resolution, high sensitivity, excellent film properties, and Improved physical properties. This application claims the benefit of Korean Patent Application Nos. 10-2009-0020384 and 10-2010-0020703, which were filed with the Korean Patent Office on March 10, 2009 and March 9, 2010, individually, The disclosures of the entire contents are cited as references for the present specification. [Prior Art] With the recent trend toward higher integration, higher density, higher reliability, and higher speed of electronic components in the field of semiconductors and semiconductor devices (especially liquid crystal display devices), considerable research has been conducted. The results take advantage of the ease with which organic materials are easily handled and purified, but even at temperatures up to 200 degrees in the component manufacturing process, 'organic polymers should be thermally stable for use in semiconductor and semiconductor components. Polyimine compounds have good thermal stability and excellent mechanical, electrical and chemical properties, and these advantages extend the use of photoresists and photosensitive insulating films comprising polyiminamide compounds in the fields of semiconductors and displays. In these cases, it is required to form a polyamidoamine compound which does not undergo film reduction and which swells when the fine pattern is formed in 201041935, which is used in the previously used polyamidamine photoresist. No need. Polyalkylene amine polymers are usually prepared by two-step polycondensation in a polar organic solvent with a diamine and a dianhydride, for example: N-mercapto-2-pyrrole N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc) or dimethylformamide (DMF) to obtain a polythyleneamine precursor solution, coated with w The polyimide precursor solution is applied to a crucible wafer or glass and the coating is cured by baking. A commercially available polyammonium product for electronic materials, which is supplied in the form of a polytheneamine precursor solution or a polyimide film, and the polyamine precursor solution is a polyimide which is supplied to a semiconductor element. The main type of amine product. Polyalkylene amine resins are used in the production of buffer coating films in semiconductor devices. In a large-scale integrated (LSI) circuit, the volume shrinkage of the encapsulated resin and the thermal expansion coefficient between the wafer and the resin cause thermal stress, resulting in a passivation film of the wafer. Cracking and metal interconnection damage. In order to solve this problem, a buffer layer composed of polyamidamine is formed between the wafer and the encapsulating material, and the buffer layer should be 10 μm to express its effect, and the thicker buffer layer has better buffering effect. , which can improve the yield of semiconductor products. The polyimide layer requires fine pattern formation, such as electrode interconnection and wire bonding pads. The via hole is formed on the poly- ugly amine layer by applying a photoresist to a non-photosensitive polyimide fiim on a non-photosensitive polyimide fiim. In recent years, many attempts have been made to form perforations using a photosensitive ph〇t〇 sensitive polyimide. The use of common non-photosensitive polyamidoamines requires the use of photoresists to process the holes to connect the wires and contact the metal interconnects, but the use of photosensitive polyimides eliminates the need for photoresist for lithography. In the latter case, the buffer coating process was shortened by about 50%, resulting in improved yield and reduced cost. The final steps in the manufacturing process of semiconductor components are also shortened, greatly improving the yield. The study of positive-type photosensitive polyamidamine is actively carried out, and the reason for the negative-type photosensitive poly-araminamide is not actively studied as follows. The first reason is that the positive photosensitive polyimide has a higher resolution than the negative photosensitive polyimide. The second reason is that the positive-type photosensitive polytheneamine is exposed to a relatively small area compared to the negative-type photosensitive polydecylene, meaning that the defect is less likely to occur. The third reason is that the use of negative-type photosensitive polyamidones can cause problems in production costs and environmental pollution (eg, wastewater treatment) because of the need for organic solvents such as N-methyl-2-pyrrolidone ( N-methyl-2-pyrrolidone, NMP) or dimethylacetamide (DMAc) is used as a developer, and the use of positive-type photosensitive poly-arasine is economically advantageous and ecologically friendly. It requires an alkaline aqueous solution as a developer. A number of methods have been developed to impart light sensitivity to polyamido resins, for example, by chemically bonding crosslinkable functional groups to polyamidamine precursors or by mixing 201041935 σ cross-linking monomers with poly-liminium precursors For preparing a photoresist composition using a polyimide resin. As another example, a quinonediazide compound is added to polyphosphamic acid (p〇1y amic acid), a polyamic ester having a side chain having an acidic functional group, or a side chain having an acidic function. Polyalkylene amine. However, the high solubility of polyaminic acid in an alkaline developer leads to a reduction in the development of the film, which requires the addition of an amine or the like. Further, poly-liminamide or poly-glycolide has high resolution, but the acidic functional group continues to exist even after hardening, resulting in poor water absorption or poor resistance to the cured film. Therefore, there is an urgent need in the art to develop high-resolution polyiminamide compounds which do not suffer from film reducti and polyimitamine which expands upon formation of fine patterns. The compound has an appropriate solubility in the test developer. SUMMARY OF THE INVENTION The present invention finds that the problems of the prior art can be solved by using at least one fluorene polyamine polymer, for example, polyamidamide polymer, polyamido acid polymer, and polyamine. The ester polymer comprises a dianhydride group having a specific structure of a repeating unit, and/or a copolymer thereof is used as an adhesive resin in the preparation of the photoresist composition. The present invention has been completed based on the results of these studies. An object of the present invention is to provide a photosensitive polyimide polymer and/or a copolymer thereof, which is added with at least one as an adhesive resin to prepare a photoresist 7 201041935 composition which has high resolution and high sensitivity. Degree, excellent film properties and improved mechanical properties, with proper solubility in alkaline developers. Another object of the present invention is to provide a positive type resist composition comprising at least one polyamidamide-based polymer and/or a copolymer thereof as an adhesive resin. [Embodiment] An exemplary embodiment of the present invention will be described in detail. The present invention provides a photosensitive polyamidamide-based polymer or a copolymer thereof. 1. Photosensitive polyamidamine-based polymer and copolymer thereof The photosensitive polyamidoamine-based polymer of the present invention and/or its copolymer may be at least one compound selected from the group consisting of polyamidite polymers and poly-brenic acid And groups of polylactide groups. The polyamimidamide-based polymer and/or copolymer of the present invention is a compound represented by Chemical Formula 1.

N—Y2-—* —b (1) wherein each Z is a tetravalent organic group derived from one or more tetracarboxylic acids, including: 3,4-dicarboxylic acid-1,2,3 4-tetrahydro-6-tert-butyl-1-naphthalene succinic dianhydride (3,4-(11〇31*1)〇乂; /-1,2,3,4-161^311> ^1'〇-6-tert-butyl-l-naphthalene succinic dianhydride 'DTBDA) or a derivative thereof, a from 1 to 150 'b from 1 to 400 'Y! is a divalent derivative derived from diamine 201041935

Divalent aliphatic or aromatic organic group of amine

化合物 The compound of Chemical Formula 1 is a polyamidamide-based copolymer comprising repeating units of a and b. The compound of the formula 1 is prepared by reacting one or more organic tetracarboxylic acids or derivatives thereof containing a Z group with an organic diamine containing a oxime group. In a particular embodiment, the compound of Formula 1 polymerizes one or more tetracarboxylic dianhydrides (generally referred to as acid anhydrides) and an organic diamine (generally referred to as diamine). The polyamine precursor is obtained, followed by dehydration ring closure. When the polyimide compound of the present invention is to be used as an adhesive resin to prepare a photoresist composition, it is required to have an appropriate solubility in an alkaline developer. For this purpose, 3,4-dicarboxylic acid-1,2,3,4-tetrahydro-6-tert-butyl-1-naphthalene succinic dianhydride (DTBDA) comprising a Z group is preferably used. The amount is from 1 to 100 mole percent, depending on the overall mole number of the anhydride used. Examples of anhydrides other than DTBDA include: aliphatic, aromatic and alicyclic livers, for example: pyromellitic anhydride, 3,3',4,4'-biphenyltetrahydro acid two needles (3,3',4,4'-biphenyltetracarboxylic dianhydride), 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ',4,4'-3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3丨,4,4'-diphenyl sulfone tetra-anhydride (3, 3,4,4,- 9 201041935 diphenylsulfone tetracarboxylic dianhydride), 2,2·bis(3,4-di-phenylene)hexaoxyisopropylidene dianhydride (2,2-bis(3,4-dicarboxyphenyl) Hexafluoroisopropylidene dianhydride), 4,4'-hexafluoroisopropylidene diphthalic anhydride, 3,3,4,4'-diphenyl sulfone tetrahydride (1,2,3,4-cyclobutanetetracarboxylic dianhydride), 1,2-di Methyl-1 , 2,3,4-cyclobutanetetracarboxylic dianhydride (1,2_dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride) ' 1,2,3,4-tetradecyl-1,2,3 , 4-, 2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanin (1,2,3,4-cyclopentanetetracarboxylic dianhydride) ' 1,2,4,5-cyclohexane tetracarboxylic acid dianhydride (1,2,4,5-cyclohexanetetracarboxylic dianhydride), 3,4-dicarboxylic acid 1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5-(2,5 - Dihydrotetrahydroolfusyl)-3-methyl-3-cyclohexanyl-1,2-dicarboxylic dianhydride (5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1 , 2-d 4&1'1) 〇 Father 丫 11. <1131111;/<11^<16), 2,3,5-trimethyl-2-cyclopentane acetic dianhydride, two Ring [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride), 2,3,4,5-tetrahydrogen. husband. 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride ' 3,5,6- 201041935 three rebel-free norbornene-2-ethanedianhydride (3,5,6-tricarboxy-2-norbornane Acetic dianhydride) and 1,2,3,4-butanetetracarboxylic dianhydride. Each of Chemical Formula 1 is a divalent aliphatic or aromatic organic group derived from a diamine. Preferably, Yi is a substituent selected from

It is a divalent aliphatic or aromatic organic group derived from a diamine, which can be used in the preparation of a general polyamidolide compound. Specific examples of such diamines include: aromatic diamines such as p-phenylenediamine, m-phenylenediamine, 2,4,6-trimethyl-1,3 -2,4,6-trimethyl-l,3-phenylenediamine, 2,3,5,6-tetradecyl-1,4-phenylenediamine (2,3,5,6-tetramethyl- l,4-phenylenediamine), 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3 , 3', 3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diamino 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethyl choline (3,4'-diaminodiphenylmethane) 3,3'-diaminodiphenylmethane), 4,4'-methylene-bis(2-methylaniline), 4,4'-methylene- Double 201041935 (2,6-diamine), 4,4'-methylene-bis(2,6-dimethylaniline), 4,4'-methylene-bis(2,6-diethylamine) (4,4'-methylene-bis(2,6-diethylaniline)) 4,4'-(2-isopropyl-6-methylaniline), 4,4'- sub Methyl-bis(2,6-diisopropylaniline)O/'-methylene-bisQj-diisopropylaniline), 4,4'diaminediphenylsulfone, 3,3'-diamine Diphenylhydrazine < (3,3,_ diaminodiphenylsulfone), benzidine, o-tolidine, m-tolidine, 3,3',5,5' - tetradecyl phenyl amide amine (3,3',5,5'-161^11161;11>,1561121<^116), 2,2'-bis(trifluoromethyl) phenylamine (2, 2'-bis(trifluoromethyl)benzidine), 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenyl) 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4] -(4-Aminophenoxy)phenyl]sulfonate (bis[4-(3-aminophenoxy)phenyl]sulfone), bis[4-(3-aminophenoxy)phenyl]((bis[ 4-(3-aminophenoxy)phenyl] suifone), 2,2-bis[4-(4-aminophenoxy) Phenyl]propane (2,2-bis[4-(4-Q resistance 111丨11〇卩11611〇\丫)卩1^11丫1]卩1>〇卩31^) and 2,2-double [4-(3-Aminophenoxy)phenyl]propane); an aliphatic diamine such as 1,6 hexanediamine ( l,6-hexanediamine), 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bis(amino) 1,4· bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 4,4'-diamine Dicyclohexyl hydrazine 12 201041935 (4,4'-diaminodicyclohexylmethane), 4,4'-diaminophenyl anilide (4,4'-diaminobenzanilide), 2,2-bis[4-(4-amine 2,2-bis-[4-(4-aminophenoxy)phenyl]hexafluoropropane), 1,3-bis(3-aminopropyl)tetramethyl-distone (1,3-bis(3-aminopropyl)tetramethyldisiloxane), bis(p-aminophenoxy)dimethylsilane, hexamethylenediamine ((11&11) ^11〇116乂乱116), ten Diburned diamine ((11&1111110 (1〇 (16. &116), 1,3-bis(4-aminophenoxy)benzene, 2,2- fl bis[4-(4-aminophenoxy) 1,2-bis[4-(4-aminophenoxy)phenyl] propane), 1,1-bis(4-aminophenoxyphenyl)cyclohexene (1,1- Bis (4-aminophenoxyphenyl)cyclohexane), bis[4-(4-aminophenoxy)phenyl]sulfone), 1,3-bis(3- 1, 3-bis(3-aminophenoxy)benzene, 5-amino-1,3,3-trimethylcyclohexylamine (5-amino-l,3,3- Trimethylcyclo-hexanemethylamine), 4,4'-bis(4-aminophenoxy)biphenyl, 1,1 bis(4-aminophenyl) ring G (l,l-bis(4-aminophenyl)cyclohexane), α,α'-bis(4-aminophenyl)-1,4·diisopropylbenzene (a, a'-bis (4) -aminophenyl)-l,4-diisopropylbenzene), 1,3-bis(4-aminophenoxy)-2,2-dimethylpropan (1,3-bis(4-aminophenoxy)-2,2 -dimethylpropane), 1,3-bis(4-aminophenoxy)benzene, 9,9-bis(4-aminobenzene) (9,9-bis(4-aminophenyl)fluorine) and 4,4-diamino-3,3'-dimercapto-dicyclohexylmethane; and mixtures thereof. 13 201041935 The acid anhydride is reacted with a diamine at 80 to 240 ° C, and preferably at 130 to 200 ° C. The reaction is carried out in a polar solvent selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, N- N-methylpyrrolidone (N-methylpyrrolidone), Ν·-ethylene. N-vinylpyrrolidone 'N-methylcaprolactam, dimethylsulfoxide, tetramethylurea' pyridine ' (dimethylsulfone), hexamethylsulfoxide, m-cresol, gamma-butyrolactone, and mixtures thereof. This reaction produces polyamic acid as a polyamine precursor. In this case, the polyamic acid is collected and separated by precipitation with a suitable solvent such as methanol or ethanol. Alternatively, polymethyleneamine can be prepared directly. The compound of the formula 1 preferably has a weight average molecular weight of from 1,000 to 1 Torr, and a glass transition temperature of from 200 to 400 ° C. The polyamine acid of the present invention is A compound as shown in Chemical Formula 2.

The compound of Chemical Formula 2 is a polyamidamine-based copolymer prepared by reacting one or more of the Z group or tetracarboxylic di anhydride with an organic diamine containing a Y3 group. . 201041935 In Chemical Formula 2, Z is a tetravalent organic group derived from one or more tetracarboxylic acids, and contains 1-100 mole percent of 3,4-dicarboxylic acid-1,2,3,4 - tetrahydro-6-tertiary butyl-1-succinic dianhydride (DTBDA) or a derivative thereof. Examples of anhydrides other than DTBDA are as defined in Chemical Formula 1. Y3 is selected from the definitions in Chemical Formula 1 and combinations thereof, and c is from 5 to 200. The reaction of the anhydride and the diamine to prepare the poly-proline is between -20 and 150. (:, preferably in the range of -5 to 100 ° C in a polar solvent selected from the group consisting of Ν, Ν 〇 甲基 dimethyl carbamide (N, N-dimethylformamide), N, N-dimercaptoacetamide (Ν,Ν-dimethylacetamide), N-mercapto 0 is N-methylpyrrolidone, N-ethylenepyrylene, N-vinylpyrrolidone, N-methylcaprolactam (N- Methylcaprolactam), dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, m-cresol, Γ-butyrolactone, and a mixture thereof 〇c represents the number of repeating units in the polyaminic acid represented by Chemical Formula 2, preferably 5 to 200. The compound represented by Chemical Formula 2 is preferably. It has a weight average molecular weight of 1,000 to 200,000 and a glass transition temperature of 100 to 300 ° C. The polyamine ester of the present invention is a compound represented by Chemical Formula 3. 15 (3) 201041935 -H Red Y3. . . /ϊΥ \ Chemical formula 3 by containing one or more of the oxime groups ^ or more The tetracarboxylic dianhydride is prepared by reacting with a gamma-containing diamine. The Y3 group is in the chemical formula 3, and the oxime is a tetravalent organic derived from one or more tetracarboxylic acids. a group comprising 1 ^ -100 mol of 3,4-dicarboxylic acid-1,2,3,4-tetrahydro-6-tertiary butyl-_ succinic acid dioxane (DTBDA) or Derivatives. Examples of g-anhydride other than DTBDA are as defined in Formula 1. Y3 is selected from gamma and chemistry as defined in Chemical Formula 1 and combinations thereof, and R is selected from the group consisting of leuco and silyl alkyl groups. The group 'field, and, and d is 5 to 200. The reaction of preparing the polyamidamide with the acid anhydride and the diamine is carried out in a polar solvent of _2 Torr to 丨, preferably -5 to 100 ° C, the polar solvent. Choose nn N, N-dimethylformamide, N, TSf-dimethyl |, , a 丫 dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl dimethyl N-methylpyrrolidone, N-vinylpyr0, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, Tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, m-cresol, γ-butyric acid -butyrolactone), and mixtures thereof. 16 201041935 d represents the number of repeating units in the polyamidamide represented by Chemical Formula 3, preferably 5 to 200. The compound represented by Chemical Formula 3 preferably has a weight average molecular weight of 1,000 to 200,000 and a glass transition temperature of 100 to 300 ° C. 聚 Polyimide polymer and/or copolymerization of Chemical Formulas 1 to 3 The object has a transmittance of 50% or higher for i_iine. When a photoreactive compound (PAC) photoreaction is generated, this high i-line transmittance increases the transmittance of the wavelength, and as a result, the photosensitive compound (PAC) has high reaction efficiency, resulting in high reaction efficiency. Higher sensitivity and resolution. In a preferred embodiment, the polyamidamide copolymer of Chemical Formula 1, the polylysine of Chemical Formula 2, and the polyamidolide of Chemical Formula 3 are shown in Chemical Formulas 4, 5 and 6, respectively.

◎ wherein Y4 and Y5 are respectively defined in Chemical Formula 1, and 丫2, and e and f represent the number of repeating units of 1 to 150 and 1 to 400, respectively.

17 201041935 wherein, as defined by γ3 in Chemical Formula 2, g represents the number of repeating units of 5 to 200, and

The photosensitive polyamidomethine copolymer of the present invention is at least one of a compound of the chemical formulae 1 to 3. That is, the photosensitive polyamidomethine copolymer of the present invention may be a copolymer of a polyamidene copolymer of Chemical Formula 1 and a polyphthalamide of Chemical Formula 2, a polyamidene copolymer of Chemical Formula 1, and Chemical Formula 3 a copolymer of polyamidamine or a copolymer of polyamic acid of Chemical Formula 2 and polyamidamine of Chemical Formula 3. The polystyrylamine copolymer of Chemical Formula 1 and the polyacetamide formed by Chemical Formula 2 are prepared by imidization of a portion of polyglycine. The copolymer of the polyamidene copolymer of Chemical Formula 1 and the polyamidamide of Chemical Formula 3 can be produced by partial imidization of a polyamidamide. The copolymer of the polyaminic acid of the chemical formula 2 and the polyamidamide of the chemical formula 3 can be produced by partial esterification of polyglycine. 2. Positive-type photoresist composition The present invention also provides a positive-type photoresist composition comprising: 100 parts by weight of at least one group selected from the group consisting of polyiminamide polymers of Chemical Formulas 1 to 3 and /or a copolymer thereof, or 1 to 99 parts by weight of at least 18 201041935 - a group selected from the group consisting of the chemical formulas 1 to 3 polyamidones-based polymers and/or copolymers thereof and the chemical formula 7 a mixture of polyamic acid.

Wherein w is a tetravalent organic group derived from -tetra(4) (tetraearb〇xyik (4) or a derivative thereof, comprising at least one group selected from the group consisting of

The group of groups is a divalent organic group derived from a diamine and is a ruthenium to ruthenium, as an adhesive resin; a photosensitive compound; and a solvent.

Specifically, the positive-type photoresist composition of the present invention comprises: at least one selected from the group consisting of photosensitive polyimiphthene polymers of Chemical Formulas 4 to 6 and/or copolymerization thereof. , or 1 to 99 parts by weight of at least one selected from the group consisting of the photosensitive polyamidamine polymers of Chemical Formula 4 to 6 and/or copolymers thereof, and 1 to 70 parts by weight of the polyamic acid of Chemical Formula 7 The mixture is used as an adhesive resin; a photosensitive compound; and a solvent. That is, the 'adhesive resin system may be a polyamidamine-based polymer and/or its co-I's selected from the group consisting of Chemical Formulas 1 to 6, or at least one poly-Asia 19 201041935 amide-based polymer And/or a copolymer thereof and a mixture of polyamido acids of Chemical Formula 7. The polyaminic acid of Chemical Formula 7 can be produced by reacting an organic diamine containing one of the w groups, an organic diamine containing a γ3 group.

The organic tetracarboxylic dianhydride containing one of the W groups is selected from the group consisting of pyromellitic anhydride, 3,3', 4,4,-biphenyltetracarboxylic acid (3) ,3,4,4'-biphenyltetracarboxylic dianhydride), 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenyl 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4·-diphenyl 13⁄4 tetraanhydride (3,3',4,4'- Diphenylsulfone tetracarboxylic dianhydride), 2,2-bis(3,4-dicarboxyphenyl)hexafluoroisopropylidene dianhydride (2,2-bis(3,4-die arboxy phenyl) hex afluoroisopropyli dene

Dianhydride), 4,4'-(hexafluoroisopropylidene diphthalic anhydride), 3,3',4,4'-diphenyltetracarboxylic acid needle ( 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride), 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl 1,2-dimethyl-1,2,3,4-eye lobutanetetrac arboxy lie dianhydride, 1,2,3,4·tetra 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-ring Pentane tetracarboxylic dianhydride 20 201041935

(1,2,3,4-cyciopentanetetracarboxylic dianhydride) ' 1,2,4,5-cyclohexanine tetra-isohexane (if 2,4,5-cyclohexanetetracarboxylic dianhydride), 3,4_ bis-acid , 2,3,4-tetrahydro-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5-(2,5-di Oxytetrahydrofuroyl)-3-methyl-3-cyclohexa-1,2-di-barred acid di-hepatic (5-(2,5-out 〇乂€^1^113^(11>〇 『1171)-3-11161;1171-3-cyclohexene-l,2-dicarboxylic dianhydride), 2,3,5-trisulphonyl-2-cyclopentanyl ethanehydride (2,3,5-tricarboxy-2 -cyclopentane acetic dianhydride), bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (bicyclo[2.2.2]oct-7-ene-2,3,5 ,6-tetracarboxylic dianhydride), 2,3,4,5·tetrahydrofurantetracarboxylic dianhydride (3,5,6-three rebel ice-freeze- 2-,5,6-tricarboxy-2-norbornane acetic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride ° Y7 The system can be any divalent aliphatic or aromatic organic group derived from a diamine. Specifically, specific examples of such diamines include: aromatic diamines such as p-phenylenediamine, m-phenylenediamine, 2,4,6-trimethyl. -1,3-phenylenediamine (2,4,6-ΊΓίιηεί1ιγ1·1,3-ρ1ιεη>^εη6£ϋαπΰηε), 2,3,5,6-θψ*-1,4-phenylenediamine (2, 3,5,6-tetramethyl-l,4-phenylenediamine), 4,4'-diaminodiphenyl ether, 3,4'-diamine diphenyl hydrazine (3, 4'-diaminodiphenyl ether), 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4 , 4'-diaminodiphenylmethyl hospital 21 201041935

(4,4'-diaminodiphenylmethane), 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyldisulfonate (3,3'- Diaminodiphenylmethane), 4,4'-adenylene-bis(2-methylaniline), 4,4'-amidino-bis (2,6 -4,4'-methylene-bis(2,6-dimethylaniline), 4,4'-methylene-bis(2,6-diethylamine benzene) (4,4'- 111 is 1^161^-bis(2,6-diethylaniline), 4,4'-arylene-bis(2-isopropyl-6-methylaminobenzene) (4,4'-methylene-bis ( 2-isopropyl -6-methylaniline)), 4,4'-methylene-bis(2,6-diisopropylaniline), 4,4'-methylene-bis(2,6-di isopropyl aniline), 4 , 4'-diamine diphenyldiphenylsulfone, 3,3'-diaminodiphenylsulfone, benzidine, o-toluidine (o -tolidine), m-tolidine, 3,3',5,5'-tetramethylbenzidine (3,3',5,5'-tetramethylbenzidine), 2,2'-double (2,2'-bis(trifluoromethyl)benzidine), 1, 4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene (1,3-bis (4) -aminophenoxy)benzene), 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl Bis[4-(4-aminophenoxy)phenyl]sulfone), bis[4-(3-aminophenoxy)phenyl]sulfone) 2,2-bis[4-(4-aminophenoxy)phenyl]propane) and 2,2-bis[4-(3 -aminophenoxy)phenyl]propane (2,2-1^5[4-(3-31111110卩116110乂>〇口116!1丫1]卩110卩3116); aliphatic diamine For example: 1,6-hexanediamine, 1,4-cyclohexane 22 201041935, dicyclohexanediamine, 1,3-cyclohexanediamine (1,3 -cyclohexanediamine) '1,4-bis(aminomethyl)cyclohexane, 1,3-bis(aminomercapto)cyclohexane (l,3-bis) (aminomethyl)cyclohexane), 4,4'-diaminodicyclohexylmethyl (4,4'-<^30^110£11〇>^1〇116Father 丫111161 : 11 &116) and 4,4'-diaminobenzinoaniline (4,4'-diaminobenzanilide); and mixtures thereof. The reaction of preparing the polyamic acid with the acid anhydride and the diamine is carried out in a polar solvent of from -20 to 150 ° C, preferably from -5 to 100 ° C, and the polar solvent is selected from N, N-

fS N,N-dimethylformamide, N,N-dimethylacetate, N-methylpyrrolidone, N - vinyl ratio N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylsulfoxide, m-cresol, gamma-butyrolactone, and mixtures thereof. 〇 i represents the number of repeating units in the polyamic acid represented by Chemical Formula 7, preferably 5 to 200. The polyaminic acid as shown in Chemical Formula 7 preferably has an elongation of up to 40%. The polylysine as shown in Chemical Formula 7 is used to protect the semiconductor from deformation or damage, and when thermal or mechanical stress is applied to the semiconductor device, the reliability of the semiconductor element due to high elongation is improved. As described above, the polyamidamide-based polymer of Chemical Formulas 1 to 6 and/or its copolymer is used as an adhesive resin, preferably having a transmittance of 50% or more for i-line 23 201041935. When a photoreactive compound (PAC) photoreaction is generated, this high i-line transmittance increases the transmittance of the wavelength, and as a result, the photosensitive compound (PAC) has high reaction efficiency, resulting in high reaction efficiency. Higher sensitivity and resolution.

The photosensitive compound refers to a compound which generates an acid when irradiated with light. The photosensitive compound is not particularly limited as long as it can generate an acid by photoreaction to increase the solubility of the exposed portion in the alkaline developer. Specifically, the photosensitive compound is preferably an o-quinonediazide compound, an aiiyi diazonium salt, a diallyl iodonium salt, or a tripropyl sulfonium hydride. Trial (atriallyl sulfonium salt), anthraquinone-nitrobenzyl ester, p-nitrobenzyl ester, trihalomethyl-substituted s-triazamethyl group -substituted s-triazine derivative) or imidosulfonate derivative. The o-quinonediazide compound is preferred in terms of sensitivity or resolution. The o-quinonediazide compound is generally an o-quinonediazidesulfonic acid ester or an o-quinonediazidesulfone amide. O-quinonediazide sulfonyl chloride and a condensation reaction obtained by carrying out a condensation reaction with at least one hydroxyl group or at least one amino group in the presence of a basic catalyst. The o-quinone azulsulfonyl-based gas system may be composed of o-quinonediazide sulfonic acid, for example, 1,2-naphthalene 1-2-heavy gas-4-acid (l,2-naphthoquinone) -2-diazide-4-sulfonic acid), 1,2- 24 201041935, 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1, 2-naphthoquinone-2-diazide-6-sulfonic acid, particularly preferably ortho-azidosulfonic acid is selected from at least the following chemical formula a compound:

Deficit: p The photosensitive compound is preferably present in an amount of from 1 to 50 parts by weight based on 100 parts by weight of the polyamidide-based adhesive resin. If desired, the photoresist composition of the present invention may further comprise a sensitizer selected from the group consisting of perylene, anthracene, thioxanthone, and rice. Michler's ketone, benzophenone and fluorene. The solvent system can be any one that can dissolve the polyamidamide-based polymer. For example, the solvent is selected from the group consisting of N,N-dimethyl form amide, hydrazine, hydrazine-dimethylacetamide, Ν-甲N-methylpyrrolidone, N-methylpyrrolidone, Ν-Ethyl 0, σ each pyridine ketone 25 201041935 (N-vinylpyrrolidone), N-methylcaprolactam, N-methylcaprolactam Dimethylsulfoxide), tetramethylurea, pyridine, bismuth

(dimethylsulfone), hexamethylsulfoxide, m-cresol, γ-butyrolactone, ethyl cellosolve, butylene cellosolve Ethyl carbitol acetate, butyl carbitol acetate, ethylene glycol, ethyl lactate, lactate Group of (butyl lactate), cyclohexanone, cyclopentanone, and mixtures thereof. The solvent is preferably present in an amount of from 30 to 90 parts by weight based on 100 parts by weight of the polyamidide-based adhesive resin. The photoresist composition of the present invention may further comprise one or more additives selected from the group consisting of dissolution rate modifiers, sensitizers, adhesion promoters, and surfactants.

The photoresist composition of the present invention is applied to a substrate, such as glass, by a suitable coating process such as spin coating, slit spin coating, roller coating, die coating. A cloth or curtain is applied, which is then exposed and developed to form a pattern. The exposure and development is carried out in a process known in the art to be suitable. The light used for the exposure process is not particularly limited, and for example, electromagnetic radiation, visible light, UV light, electron beam, X-ray or laser light can be used to illuminate the photoresist composition. 26 201041935 Examples of light sources suitable for use in exposure processes include, but are not limited to, high pressure mercury lamps, xenon lamps, carbon arc lamps, halogen lamps, cold cathode tubes for copiers, light emitting diodes, and semiconductor lasers. Thereafter, the exposed photoresist layer is coated with a developer to remove unexposed areas, leaving the desired pattern. The developer is not particularly limited. As the developer, for example, an aqueous solution of an alkali metal or a soil-based hydroxide or carbonate, a hydrogencarbonate, an aqueous ammonia or a quaternary 4 ampere salt is used. An alkaline aqueous solution of KOH is particularly preferred. The developer may comprise surfactants, antifoaming agents, organic bases (eg, benzylamine, ethylenediamine, ethylaminoethanol, tetramethylammonium hydroxide, diethylenetriamine). , tetraethylenepentamine (triethylenepentamine), morpholine (triethanolamine), organic solvent as a development accelerator (such as: alcohol, ketone, ester, ether, decylamine or internal S). The developer may be water, an organic solvent or a mixture of an aqueous test solution and an organic solvent. The overall flow of patterning is as follows. First, the photoresist composition Q is spin-coated on a substrate. The coated substrate was prebaked at 100 °C for two minutes to form a film. The film was exposed through a reticle with a high pressure mercury lamp having an exposure energy of 100-200 mJ/cm2. The exposed film was developed with an aqueous alkaline solution of KOH, rinsed with deionized water, and post-baked at 200 ° C for about 40 minutes to form a pattern. The thickness of the photoresist layer can vary depending on the intended purpose. The thickness of the photoresist layer is preferably in the range of 1 to 20 μm, but is not limited to this range. 27 201041935 The photoresist composition of the present invention exhibits positive sensitivity to high sensitivity and resolution. Further, the photoresist composition of the present invention is easily surnamed with an alkaline aqueous solution. Further, the photoresist composition is formed by a film of a predetermined pattern to promote a polyimide film having a fine shape and a high dimensional accuracy undulation pattern. The positive type resist composition of the present invention is suitable for use in the formation of a dielectric insulating film, a passivation film, a buffer coating film or an insulating film for a multilayer printed board of a semiconductor element. The positive type resist composition of the present invention is also suitable for use. The insulating film of the organic light emitting diode and the thin film transistor protective film of the liquid crystal display device are formed. The positive type resist composition of the present invention is also suitable for the electrode protective film or the organic electroluminescent device (〇rganic EL device) The formation of a semiconductor protective film. The present invention will be described in detail with the following examples. However, these examples are not intended to limit the scope of the invention. EXAMPLES Example 1: Preparation of Polyimide Copolymer of Chemical Formula 1 11.0 g of 2,2-bis(3-amino-4-hydroxyphenol)hexafluoropropane (2,2-bis(3-amino-4) -hydroxyphenyl)hexafluoropropane) and 40 g of γ-butyrolactone were placed in a 1 mL round bottom flask. The mixture was completely dissolved with slow agitation. 10.7 g of 3,4-dicarbamic acid-1,2,3,4-tetrahydro-6-tert-butyl-1-naphthalene succinic dianhydride (DTBDA) was slowly added to the flask in a water bath while maintaining the The flask was at room temperature. The resulting mixture was stirred at room temperature for 16 hours, after which time 7 g of toluene was added. After the flask was equipped with a Dean-Stark distillation gate, the mixture 28 201041935 was heated to reflux at 140 ° C for 3 hours to remove moisture. The solution was cooled to room temperature and slowly poured into a methanol/water (1/4) solution. The obtained solid was dried in a vacuum drying oven at 40 ° C for one day to yield 16 g of soluble polyamidamide resin. The IR peak corresponding to the polyamidamine was observed. The polyacrylamide resin was found to have a weight average molecular weight of 40,000 and a degree of polydispersity index (DIDI) of 1.6 as measured by gel permeation chromatography (GPC). Example 2: Preparation of 4,4'-diaminodiphenyl (4,4'-oxydianiline) of 6 g of the polyamidofluoride of Chemical Formula 2 and 40 g of γ-butyrolactone by γ-butyrolactone The sequence was placed in a 1 mL mL round bottom flask. The mixture was completely dissolved with slow agitation. 10.7 g of 3,4-dicarboxylic acid-1,2,3,4-tetrahydro-6-tert-butyl-1-naphthalene succinic dianhydride (DTBDA) was slowly added to the flask while maintaining the flask The jacket temperature of the reactor was at 20 °C. The resulting mixture was mixed for two hours to fully react. Stirring was continued for 16 hours at room temperature to produce poly-proline. The IR peak corresponding to the poly-proline was observed. It was found by gel permeation chromatography (GPC) 醯 that the polyglycolic acid had a weight average molecular weight of 50,000 and a polydispersity index (PDI) of 1.6. Example 3: Preparation of 7.5 g of N,N'-bistrimethylsilylbenzene-l,4-diamine and 40 g of polyammonium ester of Chemical Formula 3 Gamma-butyrolactone was sequentially placed in a 10 mL jacketed round bottom flask. The mixture was completely dissolved with slow agitation. 10.7 g of 3,4-dicarboxylic acid-1,2,3,4-tetrahydro-6-tert-butyl-1-naphthalene succinic dianhydride (DTBDA) was slowly added to the flask at 29 201041935 while maintaining the The flask was jacketed at 20 ° C outside the reactor. The resulting mixture was thoroughly reacted after stirring for two hours. Stirring was continued for 20 hours at room temperature to produce a polyamidamide. Observe the IR peak corresponding to the silyl ester. As measured by gel permeation chromatography (GPC), it was found that polyammine ester had 4 〇, the weight average molecular weight of 〇〇〇 and the degree of polydispersity index (PDI) was Example 4: Preparation of Chemical Formula 7 73.3 g of 4,4'-diaminodiphenyl ether (4,4'-oxydianiline) and 300 g of γ-butyrolactone were placed in a 1 L jacket circle. In the bottom flask. The mixture was completely dissolved with slow agitation. 55.8 g of 3,3,,4,4'-3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride was slowly added to the flask while maintaining the temperature of the flask outside the reactor (jacket temperature)) at 20 °C. The resulting mixture was thoroughly reacted after stirring for two hours. Stirring was continued for 16 hours at room temperature to produce poly-proline. ◎ Observe the IR peak of the corresponding polyglycolic acid. As measured by gel permeation chromatography (GPC), the polyglycolic acid was found to have a weight average molecular weight of 50,000 and a polydispersity index (PDI) of 1.6. Example 5: Preparation of a photoresist composition (polyimine composition) 0.5 g of a diazolamhthoquinone ester compound (TPPA 320, OH and OD based on selectivity selectivity OD/( OD+OH) = 2/3) was added as a photosensitive compound and 4 g of γ-butyric acid 30 201041935 lactone (γ-butyrolactone, GBL) as a solvent to 1.6 g of the preparation prepared in Example 1. Soluble polybendamine. The mixture was stirred at room temperature for one hour. The reaction mixture was filtered through a filter (pore size = 1 μm) to prepare a photoresist composition. Example 6: Preparation of a photoresist composition (polyimide/polyamidoxime blend) 8·2 g of the soluble polyamidamine prepared in Example 1 and 27.5 g of the example 4 The prepared polylysine is mixed together. To the mixture, 4.7 g of diazonaphthoquinone ester compound (TPPA 320, OH and OD based on selectivity selectivity 0D/(0D+0H)=2/3) was added as the photosensitive property. The compound and 18 g of γ-butyrolactone (GBL) were used as a solvent. The mixture was stirred at room temperature for one hour. The reaction mixture was passed through a filter (hole size = 1 μm) to prepare a photoresist composition. Q Comparative Example 1: Preparation of Polyimide Copolymer 11.0 g of 2,2-bis(3-amino-4-hydroxyphenol)hexafluoropropane (2,2-bis(3-amino-4-hydroxyphenyl) using THNDA Hexafluoropropane) and 40 g of γ-butyrolactone were sequentially placed in a 100 mL round bottom flask. The mixture was completely dissolved with slow agitation. 9.0 g of 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (4-(2,5-(dioxotetrahydrofur an) -3-yl)-1,2,3,4-tetrahydronapht halene-l,2-dicarboxylic anhydride,THNDA) was slowly added to the flask in a water bath while maintaining the flask at room temperature. The resulting mixture was in Room 31 201041935 After stirring for 16 hours, 7 g of toluene was added thereto. After the flask was charged with a Dean-Stark distillation gate, the mixture was heated under reflux at 140 ° C for 3 hours to remove water. The solution was cooled to room temperature and slowly poured into a methanol/water (1/4) solution. The obtained solid was dried in a vacuum drying oven at 40 ° C for one day to yield 16 g of soluble polyamidamide resin. The IR peak of decylamine was measured by gel permeation chromatography (GPC) and found to have a weight average molecular weight of 40,000 and a polydispersity index (PDI) of 1.5. Comparative Example 2: Preparation Photoresist composition (THNDA polyamidamine composition) 0. 5 g of diazo naphtholene S is a compound (diazonaphthoquinone ester compound) (TP PA 320, OH and OD are based on selectivity selectivity OD/(OD+OH) = 2/3) as the photosensitive compound and 4 g of γ-butyric acid (GB-) To the solvent was added 1.6 g of the soluble polyamidamine prepared in Comparative Example 1. The mixture was stirred at room temperature for one hour. The reaction mixture was filtered through a filter (pore size = 1 μηι) to prepare a photoresist. Composition 1. Experimental Example 1: Evaluation of physical properties of the film Each of the photoresist compositions of Examples 4 to 6 was spin-coated on a glass substrate and fired on a hot plate at 180 ° C for 60 minutes under a nitrogen stream. And calcined at 300 ° C for 60 minutes to form a 10 μη thick polyimide film. In a high pressure steam sterilizer (autoclave), at 2.3 atm, 125 ° C under pressure cooking 32 201041935 (Pressure cooking Treatment, PCT) The poly-nitramine film was allowed to stand for 30 minutes to remove the film from the glass substrate. The polyimide film was cut into test pieces having a width of 1 cm and a length of 8 cm. The tensile properties were measured. The results are shown in Table 1. Table 1 Tensile strength (MPa) Elongation (%) Coefficient (GPa) Example 4 160.4 126.5 2.9 Example 5 108 10.7 3.2 Example 6 127.6 32.8 3.0 As shown in Table 1 and Figures 1 and 2, polyiminamide was used as the adhesive. Resin Example 5 The photoresist composition (Fig. 1) has high resolution and exhibits excellent mechanical properties, including tensile strength. In addition, the use of a polyamine/polylysine blend as a binder resin shows that the pattern of the photoresist composition of Example 6 indicates that the pattern may have better mechanical properties. 2. Resolution and Sensitivity Evaluation Each of the photoresist compositions of Examples 5, 6 and Comparative Example 2 was spin-coated on a 4 Å wafer and prebaked on a hot plate for 2 minutes to form 150 μm. Thick photosensitive film. The prebaked crucible wafer is adhered to a reticle under vacuum and exposed using an I-line optical stepper (I-line stepper) to increase the exposure energy from 100 mJ/cm 2 at a rate of 5 mJ/cm 2 . 600 mJ/cm2. The exposed wafer is at 23. (: 2.38 wt% tetradecyl ammonium hydroxide aqueous solution was developed for 80 seconds, washed with deionized water for 60 seconds, and dried without being exposed while leaving the unremoved portion to form a pattern. The patterned ruthenium wafer was under a nitrogen stream The substrate is fired on a heated 33 201041935. Specifically, the patterned tantalum wafer is slowly heated from room temperature to 180 ° C for about 3 minutes at 180 ° (: 60 minutes, 30 minutes slowly heated to 300 °) C, and maintained at 300 ° C for 60 minutes. The calcined film has a thickness of 1 〇 μηι. The pattern has a line width of at least 3 μηη, indicating a high resolution of the photoresist composition. An electron micrograph of a high resolution pattern formed using the photoresist compositions of Examples 5 and 6. The pattern formed using the photoresist composition of Example 5 has a sensitivity of 45 μm/cnr and 90% of the residual film ratio after development. In contrast, the pattern formed by using the photoresist composition of Comparative Example 2 (which was prepared by using a polytheneamine copolymer of THNDA as a monomer) was 55 μm. Sensitivity of /cm2 and 82% residual film ratio after development The residual film ratio of Example 5 and Comparative Example 2 was considered, and the photoresist composition of Example 5 was adjusted (that is, the photoresist composition of Example 5 was assumed to have the photoresist composition of Comparative Example 2). The same residual film ratio after development), it is expected that the photoresist composition of Example 5 will exhibit higher sensitivity than the photoresist composition of Comparative Example 2. The higher light sensitivity of the photoresist composition of Example 5. The sensitivity is due to the higher transmittance (95%) of the polyamidamide copolymer using DTbdA, which is higher than the transmittance (87%) of the polyamidamide copolymer using thNDA, indicating Example 5 The photoresist composition has a higher light efficiency. This difference is due to the presence of a bulky third butyl group which hinders the stacking of polymer chains and prevents charge transfer from occurring. Furthermore, the hydrophobicity of the third butyl allows examples. The photoresist composition of 5 remains after development without being removed 'the residual film of the photoresist composition of Example 5 34 201041935 film ratio' is higher than the photoresist of Comparative Example 2 using THNDA The composition, which ensures a room for further improvement in sensitivity. It is apparent that the photoresist composition of the present invention exhibits high resolution, excellent film properties, and improved mechanical properties required for forming a semiconductor buffer coating film. [Schematic Description] This and/or the present invention Or other features and advantages will become apparent from the following description of the embodiments and the accompanying drawings, wherein: Figures 1 to 2 are the patterns formed by using the compositions prepared in Examples 5 and 6, respectively. Electron microscopic image. [Main component symbol description]

Claims (1)

201041935 VII. Patent application scope: h photosensitive polyacrylic amine polymer, which comprises at least one compound selected from the formula 1: roo - L person" [Hi 丫丫Ν Υι L 0 0 ” a ΓϊΥΊ L 0 〇J b- (1) Each of Z is a tetravalent organic group derived from one or more tetracarb〇xylic acids, and includes: a percentage of u moles of 3 bis-acid-1. 2,3,4-tetrahydro-6·tert-butyl-1-naphthalene succinic dianhydride (34dicarb〇xy_l,253,4-tetrahydro-6-tert-butyM-naphthalene succinic dianhyddde' DTBDA) or Derivatives, & from 丨 to 15〇, to 4〇〇, H0 0H Υι is a divalent organic group derived from a diamine and is selected from , 0H, and Y2 are divalent aliphatic or organic groups derived from diamine; compounds as shown in Chemical Formula 2; aromatic 36 201041935 L Ο 0 ”c (2) wherein, as defined in Chemical Formula 1, Υ3 is selected from Υι and Υ2 and combinations thereof defined in Chemical Formula 1, and c is from 5 to 200; and a compound represented by Chemical Formula 3 Group Wherein, as defined in Chemical Formula 1, Υ3 is as defined in Chemical Formula 2, and d is from 5 to 200 ° 2. The photosensitive polyamidamine-based polymer according to claim 1, wherein the chemical formula 1 The compound shown has a weight average molecular weight of from 1,000 to 100,000. 3. The photosensitive polyamidolide-based polymeric Q according to claim 1, wherein the compound of the chemical formula 1 has a glass transition temperature of from 200 to 400 °C. 4. The photosensitive polyamidolide-based polymer according to claim 1, wherein the compound of the formula 2 and the compound of the formula 3 have a weight average molecular weight of 1,000 to 200,000. 5. The photosensitive polyamidamide-based polymer according to claim 1, wherein the compound of the formula 2 and the compound of the formula 3 have a glass transition temperature of 100 to 300 °C. ° 37 201041935 6_ A photosensitive polyamidamine-based polymer comprising at least one compound selected from the group consisting of Chemical Formula 4: ,~丫5- 〇 OH II I Η I and HO 〆 / 0H, Y5 is a divalent aliphatic or aromatic organic group derived from a diamine, and e and f are from 1 to 150 and 1 to 400, respectively; a compound represented by Chemical Formula 5; a group consisting of compounds represented by Chemical Formula 6; 38 201041935 (6) wherein hydrazine is a divalent organic group derived from a diamine, and R is selected from the group consisting of an alkyl group and a silyl alkyl group, and h is from 5 to 200.光敏 〇 . 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏 光敏Free of polyammonium-based polymers of the group of Chemical Formulas 4 to 6 as described in claim 6 of the patent application. 8. A positive type resist composition comprising an adhesive resin, a photosensitive compound, and a solvent: wherein the adhesive resin comprises at least one group selected from the group consisting of Chemical Formulas 1 to 3 as described in claim 1 The polyamidamide-based polymer, and at least one polyiminamide-based polymer selected from the group consisting of Chemical Formulas 4 to 6 as described in claim 6 of the patent application, and/or a copolymer thereof. 9. The positive-type photoresist composition according to claim 8, wherein Υ7· (7) The tetravalent organic group of the derivative and containing at least one of 1 to 1 mole percent 39 201041935 Why is Y7 derived from the divalent organic group of the diamine and A 5 to 200, based on 100 parts by weight of the adhesive resin. 10. The positive type resist composition according to claim 9, wherein the polyamine acid amount as shown in Chemical Formula 7 is from 1 to 70 parts by weight based on the total adhesive resin. The positive-type photoresist composition according to claim 8, wherein the photosensitive compound and the solvent are present in an amount of from i to 5 parts by weight and from 3 to 90 parts by weight, respectively, based on the adhesive resin. 100 parts by weight. 12. The positive-type photoresist composition as described in claim 8 which has a transmittance of 5% by weight or more to Mine of the adhesive resin 〇13. The positive type resist composition according to item 9, wherein the polyamic acid as shown in Chemical Formula 7 has an average or higher elongation. 14. The positive-type photoresist composition according to claim 8, wherein the photosensitive compound is at least selected from the group consisting of: a compound: 40 201041935 The positive-type photoresist composition of claim 8, wherein at least one of the solvents is selected from the group consisting of N,N-dimethyl decylamine (Ν, Ν- Dimethylformamide) N,N-dimercaptoamine (N-methylpyrrolidone) N-methylpyrrolidone (N-methylpyrrolidone) N-vinylpyrylidene (N-vinylpyrrolidone) ), N- • N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylhydrazine (dimethylsulfone), hexamethylsulfoxide, m-cresol, γ-butyrolactone, ethyl cellosolve, butyl cellosolve, Ethyl carbitol acetate, butyl carbitol acetate, ethylene glycol, ethyl lactate, butyl lactate, A group consisting of cyclohexanone, cyclopentanone, and mixtures thereof. 41