TW201024336A - Water soluble photo-sensitive polyimide polymer, process for preparing the same, and photoresist composition containing the same - Google Patents

Abstract

The present invention relates to a water-soluble photo-sensitive polyimide polymer, its preparation, and photoresist composition containing the same. The water-soluble photo-sensitive polyimide polymer is characterized by having a repeat unit represented by the following formula (I): (I) [wherein, R1 represents a tetravalent organic group; R2 represents a trivalent or tetravalent organic group which is optionally substituted with carboxyl group; R3 represents a divalent to tetravalent organic group; A represents OH or COOH group; R4 and R5 are the same or different and independently represents alkylene group containing 1-20 carbon atoms, arylene group, aralkylene group, or arylene-oxy-alkylene group containing 6 to 20 carbon atoms; R7 and R8 are the same or different and independently represents hydrogen, halogen, carboxyl, linear or cyclic alkyl containing 1-20 carbon atoms, aryl, alkaryl, or aralkyl containing 6 to 20 carbon atoms; R9 represents a hydrogen atom or an alkyl group having 1-6 carbon atoms; x represents 1 or 2; y represents 0, 1, or 2; a, b, and n each represent an integer of 1 or more than 1; m and k each represents an integer of 0 or more than 0].

Description

201024336 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a water-soluble photosensitive polyimide pigment polymer and a process for the preparation thereof. In detail, it is a water-soluble salty imide polymer which has good solubility in organic solvents and alkaline aqueous solutions, and has excellent heat resistance, flexibility and electrical insulating properties after being formed into a crucible, and can be widely used in the electronics industry. In the semiconductor process, in the semiconductor process, there is the use of photolithography etching technology to draw lines on the substrate, and the technology on the side of the 赖 彡 必 必 必 , , , , , , , , 脂 脂 脂 脂 脂 脂 脂 脂 脂The exposed printed circuit board or the unexposed portion of the printed circuit board may be removed by an alkali solution or the like after being exposed through the reticle having the desired ray. Place

Wherein R is a hydrogen atom or a fluorenyl group. reaction

Further, the polydiimine precursor of the above formula (1) is obtained by reacting with the tetrabasic dianhydride monomer 4 201024336. The unit f ίϋ6025113 discloses a polyimine precursor having an early position in the following formulas (3) and (4): repeating - RJ-CONH-R2_ (2 l of °°〇)

(3) (4) 参^T,%ZZ7Z%^ : is a water-soluble photosensitive polyimine polymer with hydrazine type, its characteristics

N 2 ^/r M 6 II -O—C—R——CIO N H OA Vo ^ , IRf V_J OA Yo R3IAV - N ΟΛ^ΥΟ OA Yo 3⁄4 3

R4 T N o A VMO R OA Yo N a o H3.iH3 c-sIc Η3/^ν H3 cIsIc 5 201024336 r9 R6= -CRf=CR8-

R9 or

i ancient m contains 4 _ upper carbon atom% of the machine base is a trivalent or tetravalent organic group, its _L can be filled with filament; & table, showing OH or C00H base '· & and R5 can be the same ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ Or different and uniquely selected from the group consisting of a straight chain or a ring green group containing 1_2G carbons, containing (four) carbon ❹ f f f , , , ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; X represents an integer of 1 or 2; y represents the whole b and η of 〇, 丨 or 2 represents an integer greater than or equal to 丨; m and k represent an integer greater than 〇 ' The above repeating units may be a stagnation polymerization Can be a random aggregation. The weight average molecular weight of the water-soluble photosensitive polyamidene polymer converted to polystyrene by gel permeation chromatography (GPC) _ about 10,000-300,000, 2 〇, 〇〇〇^15 〇, 〇 〇〇, ίi Μ (4).85, and its 5% fine temperature loss (Td A) is lower than 350 C, preferably lower than 340 ° C. In the invention, the above-mentioned intrinsic viscosity is prepared by formulating the polymer concentration as a solution of O.Sg/dL, using N•methyl D to the side of the _" as a solvent, and using a capillary viscosity^(Ubbdohode V1Scometer) Determination, and then calculate the value of its intrinsic viscosity by the following formula: V inh = ln (t / t0) / 0.5 (g / dl) where t0 -; the amount of the grain through the viscosity meter up and down two sets of blank time (seconds) The time (seconds) in which the solution passes through the upper and lower scales of the viscometer. The above 5% thermal decomposition temperature (Td (95%)) is the temperature at which the resin is thermally decomposed by 5% using a thermogravimetric analyzer (TGA). Water; the solution of the valley photosensitive photopolymerizable polyimide in an aqueous solution, and excellent in the film formation (film thickness: 10 to 25 μm), the film (size: 9*5.5 cm2) The dissolution time in a 1000 ml aqueous solution of sodium carbonate is less than 2 minutes 6 201024336 'shows good solubility in aqueous alkali solution. The invention further relates to a method for preparing a heavy-weight polyimine polymer having the following formula (1): Unit of water / fucking sexy

OA VMO R OA Yo N N Elc rh 2

J >lcIRIcIo OA vno R OA Yo 4 f ΟΛ ΫΠΟ R onMU^ ΥΠΟ οη3ιη3 chI-siIc a ?Η3ίιί

R r9 (I) -CRt=CR8-

R9 or

ί/ship 1 it has a tetravalent organic group on the carbon atom; it is converted to a trivalent or Γΐϋ, and a silky % means a 2 to 4 organic ruthenium; the heart and the heart can be the same or different, Do not look at the niche R with 6 to 20 carbon atoms of the extended aryl group, 'oxyl extension wire; R8 can be smoked or published as a choice g, halogen, county, 1-20 carbon linear or ring An alkyl group, an aryl group containing 6_2〇, a silk group and an aromatic yarn; R9 represents a hydrogen atom or a burning atom containing 6 to 6 specific atoms; X represents an integer of 1 or 2; y represents 〇, 丨Or an integer of 2, · ab and η; ^ is greater than or equal to the integer; m & k means an integer greater than ]] • each repeat in the shoulder may be block polymerization or random polymerization; the method includes the following steps : The acid dianhydride is reacted with a diamine having a plurality of groups and/or a plurality of functional groups to obtain a poly-diamine which has a carboxyl group and/or a hydroxyl group in the main chain. The amount of the ear # is an acid dianhydride: ^2 0.8-1 : 1.2 〇 2) heating and cyclizing the polyproline precursor having a carboxyl group and/or a hydroxyl group in the main chain obtained in the above (a) , get the main 201024336 polyimine having a carboxyl group and/or a hydroxyl functional group in the chain; and ΛR6 p Ο (Π) R9 ❹

Rg (wherein R6=-CRt=CR8 phase or different and independently selected from the group consisting of gas, dentate, ^ base, aryl group containing γ ίίίϊ (four) carbon atoms, aryl group and aromatic burning, % table a non-hydrogen atom or an alkyl group containing ruthenium to 6 carbon atoms; a polyvalent single-line from the polyacid method of the acid group, the use of the county and/or the base used in the above step (8) can be used only A diamine having a hydroxyl group functional group, and having only a diamine having a basic character of the base group. When only the starting diamine is used, 'only the / it polymerization unit in the above formula (1) can be obtained; and the value of m can be controlled by controlling the content of the dianhydride (11), such as dianhydride (Π) When the equivalent is equal to the hydroxyl equivalent, m becomes G, and when the slit equivalent is larger than Ϊ (Π), m becomes greater than G. When using a diamine having a polar group and a thiol group, 'A' in the above formula 1 can be used to represent 0H and CO〇H - & / and the value of m can be controlled by controlling the content of the dianhydride (II), For example, when the (2) equivalent of the liver is equal to the base equivalent, 'm becomes G, and when the equivalent is greater than the equivalent of the monobasic anhydride (II), the melon becomes greater than 0^~t. In the method of the invention, the silk used in the above step (8) And/or one of the amines of the Kiru fa soil may also be partially replaced by a diamine having a dream oxygenating functional group. The diamine having an oxime-oxygen functional group in the present invention is the following diamine:

S 201024336

H2N—(CH2)3~Si-〇—Si—(CH2)3—ΝΗα, CHj CH3

(2) CHa 013 H2N—(CH2)4-—Si-0~Si-(CHa)4-NH2, ch3 ch3 ch3 ch3 HjN—(CH^h—Si—O—Si—(CH2)3-NH2, ( 3)

Ch3 ch3 -Sh-O-Si-C CH3 ch3 (6) ch3 ❹ In the method of the present invention, (7) used in the above step (8), the second ship having the rebel base and//new base energy base is cut off, without damaging the present invention. The final polyimine resin is used in combination to produce a diamine commonly used in the polyamidene resin. In the method of the present invention, the condensation reaction of the step (8) is carried out in the method of the present invention. In the above step (8), the material is tender ==== There is no particular limitation on the case of the stalk i, but as long as the total amount of the dicarboxylic acid dianhydride to the diamine, the ear! The ratio may be within the above range, but it is preferred to have the diarrhea functional group 201024336 敎 5~6G 摩尔%, more 1G 〜4G%, preferably the agent ff ί 可 朗 can be used as light _ And as a photoresist for the sense = r; S: 4 main (A) and a soluble photosensitive polyimide resin composition, which comprises a repeating monomorphic water-soluble (tetra) sub-estiate; (8)

ϋ ϋ ^ Early riding; and (〇光起_. Its towel age (Α): The ratio of the weight of the knife is 100: 1〇~2〇〇, preferably 1〇〇: 4〇~1〇〇. When the component (4) is 100 parts by weight/°, the ratio is 0.1 to 15.0% by weight, preferably 1.0 to 5.0% by weight. [Embodiment] The present invention is used for preparing a poly Examples of the tetracarboxylic acid di-field used in the amine method step (&) may, for example, be (but are limited to) 2,2,-bis(3,4-diphenyl)hexafluoropropane dianhydride (6FDA) ), pyromellitic dianhydride (pmda), 4,4, oxy phthalic anhydride (ODPA), 3,3', 4, 4, biphenyltetracarboxylic dianhydride (bPDA), 3, 3, , 4,4,_benzophenone tetracarboxylic dianhydride (BTDA), ethyltetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetrareic acid dianhydride, 2, 2', 3,3'-dibenzophenone tetracarboxylic dianhydride, 2,2,3,3,-biphenyltetra, acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane II Anhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl) Needle, 1,1_bis(2,3-dicarboxyphenyl)ethane dianhydride, double (2,3_two Base phenyl) 曱 二 二 ' 'bis (3,4-dicarboxyphenyl) decane dianhydride, 4,4, · (p-phenylenedioxy) dicarboxylic acid dianhydride, 4, 4 '- (between - phenyldioxy)dicarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, ι, 2, 5, 6· Naphthalene tetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic acid di Sf ' 3,4,9,10-naphthalene tetrazoic acid II,2,3,6,7-蒽4 a bismuth dianhydride and a 1,2,7,8-phenanthrenetetracarboxylic dianhydride, etc. The dianhydrides may be used singly or in a mixture of a plurality of them. Among them, a method for preparing a polyimine in the present invention is preferred. Examples of the diamine having a carboxyl group and/or a hydroxyl functional group used in the step (a) include, but are not limited to, for example, 3,5-diamino group 201024336 benzoic acid (0 dip 2), 3, 3, _ Dihydroxy-44, the cap of the present invention is prepared, etc. The diamine of the functional group can be exemplified by, for example, oxime 3Hi having oxydicarbone (DSI) and 1,3 bis (4-amine). Sense-aminopropyl)_U,3,3-tetradecylbis(3-aminopropyl)-13_dimethyl methacrylate <^1 mountain 3,3_tetramethyldioxane, 1 ,3-based>U,3,3-tetramethyldi:oxime, ketone, U-bis(3-amino ❹ ❹ The method for preparing the poly-imine of the present invention is based on the step group and/or Cheng Weihong 1 and has a sulphamine, and can be exemplified by a terminal diamine di- oxy) (APB), 4, 4, - bis ( 4-aminophenoxyl l = B), bis[4·(3_aminophenoxy)phenyl]methyl, ίί, 乙二1广双[4_(3-hexenyloxy)phenyl] Acetyl, 2:2 _ _ (上基双 (4) 3 phenoxy) phenyl] butyl, with double L, Li basic oxy group (a) mountain ^ ^ fluoropropyl appearance ^ '- shuangji amine phenoxy Bismuth [4·(3_amine), phenyl, bis[4-(3-aminophenoxy)phenyl]di-bis[4_(3·aminophenoxy)phenyl] Amidene, bis[4_(3-aminophenoxy)benzene, bis[4-(3.aminophenoxy)phenyl; The above diamines may be used singly or in combination. In the step (a) of the method for preparing a poly-imine of the present invention, the reaction of the dianhydride with the diamine can be carried out in an aprotic polar solvent, and the species of the aprotic polar solvent is not particularly limited as long as it is not reacted with the reactants and The product can be reacted. Specific examples include hydrazine, hydrazine-dimethylacetamide (DMAc), hydrazine-methylpyrrolidone (νμρ), hydrazine, hydrazine-dimethyl ketoamine (DMF), tetrahydrofuran (THF). ), dioxins, chloroform (qjc13), dichloromethane, etc. Among them, N-methylpyrrolidone (NMP) and N,N-dimethylacetamide (DMAc) are preferably used. ^ In the method step (a) of the invention for the production of polyimine, the reaction of the diacid and diamine 201024336 is generally carried out at room temperature to 90 ° C, preferably 30 to 75 V. In the method of imine, it is carried out in steps. For example, maleic anhydride, substituted maleic anhydride t monoanhydride (phthalic acid) phthalic anhydride or the like can be exemplified. The anhydride-substituted methylene is adjacent to the soluble photosensitive polyimide resin of the present invention. The composition of the simple ___ is a dilute _ function containing an ethylene functional group, so it also contributes to the hardening of the sterol trimethyl group after the composition is illuminated. Acrylic _ purpose and so on. Li Wu - methyl (four) _, two quarters of the four doses ^ invented the fragrant Yalin fat in the seasoning light _, light, the object / Lang's Sishou County is in the heat of the 7b far ultraviolet light, electron beam and The 卞 卞 会 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生 生Anthraquinones such as silver chlorophenyl)·4,4,,5,^ 肆(4-B|Γα ^Miwa, 2,2'_bis(2_bromophenyl)-4,4,,5 ,5,- 卿,,5,5'-four stupid-U'4 Mic::2:2, double two and 2,2'-double (2,4" stupid eight, such as triphenylphosphine oxide (τρ〇' can be purchased from basf △ Division), such as bis (2,4,6-trimethylphenyl fluorene) phenyl lanthanum oxide (four) Yan 8i9 12 201024336 (IR819) 'Jing from Ciba Geigy Company An alkylene network such as i-cyclohexyl phenyl ketone [as purchased from Ciba Geigy, Inc., Irgacure 184 (IR184), 2-mercaptodecyl σ-septenyl)-2- holly- 1-propan-1-one [for example, Irgacure 907 (IR907) from Ciba Geigy Co., Ltd.], etc. Examples of the photoinitiator are, for example, Benzoin-based photoinitiators such as benzoin and benzophenone. In view of methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, mercapto-2-phenylmercaptobenzoate, and the like. Further, examples of the initiator include, for example, an acetophenone-based structure such as 2,2-dimethoxy-2-phenylacetophenone [e.g., from aba Gdgy Co., Ltd. with !rgacure 65i (IR651)], ginseng 2- Hydroxy-2-indenyl-1 -Phenylpropanoid, μ(4_isopropylphenyl)_2_transyl-2-methylpropanone, 4-(2-carbylethoxy)phenyl-(2_base: Propyl)ketone, fluorenyloxyacetophenone, 2,2-diethoxyacetophenone, 2-mercapto-2-diamine, small (4-morpholinylphenyl)butane-1 -ketone, 2,2-dimethoxy·ι,2·diphenylethyl_ι_辋, 4_azidoacetophenone, 4_azidoylide> acetophenone, and the like Examples of photoinitiators include, for example, benzophenones such as benzophenone, 4,4, bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino). Benzophenone, 3,3'-dimethyl-4_methoxybenzophenone, and the like and the like. Examples of a photoinitiator include, for example, a photoinitiator having an α-diketone structure. , for example, glycerin vinegar, diphenyl sulfonate carboxylic acid vinegar, mercapto benzhydryl carboxylic acid vinegar, and the like; and a photoinitiator having a polynuclear brewing structure, such as 2, ethyl hydrazine, 2 _ San Dingru, 1,4·Cai Zang, etc. and similar street organisms, 'xanthone' structure, light class, ketone, thioxanthone, 2,4_diethylthioxanthone, 2-chlorothiazide Tons of ketones and the like Structured photoinitiators such as 4-diazodiphenylamine, 4·diazo-4,_曱4_weilkoxydiphenyl, and _derivatives; 2:(4, ϋ ' - 曱Oxystyryl M,6-bis(trichloromethyl)-S-triterpene, a certain group, bis (trichloromethyl), triterpenoid, 2-(2, _ _ 4, fluorenyl Benzene, -bis(dichloromethyl)-triazine, 2-(2,-nonylphenylene) 4,6-bis(trichloromethyl 13 201024336)-S-triazine, and the like, and similar derivatives. These photoinitiators may be used singly or in combination of two or more. The photoinitiator (C) is used in an amount of 0.1 to 15.0% by weight, preferably 1.0 to 5.0% by weight, based on 100 parts by weight of the component (A). The present invention will be further illustrated in the following examples and examples, which are intended to be illustrative only and not to limit the scope of the invention. Synthesis Example 1 41. 5 g (0.1 mol) of 2,2,·bis-[4-(4·aminophenoxy)phenyl]propane (BAPP) and 9.14 g (0.06 mol) 3,5-Diaminobenzoic acid (DABZ) and 350 ® grams of N-methyl fluorenone (NMP) were placed in a 1 liter glass reaction flask 'with vigorous stirring at room temperature. After adding 88.48 g (0.2 mol) of 2,2,-bis(3,4.dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) in a reaction flask for 1 hour, then 8.43 g (0.039 mol) was added. 3,3'-Dihydroxy-4,4'-diaminobiphenyl (HAP), stirred at room temperature for 3 hours. Then, 50 g of toluene was added, and the temperature was increased to 150 ° C for 24 hours to carry out a hydrazine imidization (cyclization) reaction to obtain a polyimine with an OH group, followed by the addition of 3.92 g (0.04 mol) of malt. The imine (MA) ' continued to react at room temperature for 3 hours. Then, the resin was poured into a large amount of decyl alcohol to precipitate, and 136.2 g of a polyimine polymer (PI-1) was obtained (yield: 90.01%, IV was 0.81, Td (95%): 340. 〇. 〇 Synthesis Example 2 • 15.215 g (0.1 mol) of 3,5-diaminobenzoic acid (DABZ) and 200 g

Place in a 1 L glass reaction axe and stir vigorously at room temperature. Add 44.42 g (0.1 mol) of 2,2'-bis(3,4-dicarboxyphenyl)-hexafluoropropane dianhydride (6FDA) and 32.22 g (0.1 mol) of 3,3,4,4 - Diphenyl fluorenone tetracarboxylic dianhydride (BTDA), after stirring for 1 hour in the reaction, adding 21.19 g (0.098 mol) of 3,3,-dihydroxydiaminobiphenyl at room temperature for stirring 3 hour. Then, 3 g of toluene was added, and the temperature was raised to 150 ° C for 24 hours to carry out a hydrazine imidization (cyclization) reaction, and a polyimine with an OH group was obtained, and then 5 88 g (〇〇) was added. The maleic anhydride of 6 moles was allowed to react for 3 hours at room temperature. Then, the resin was poured into a large amount of methanol to precipitate' to obtain 112.7 g of polyamidene polymer milk 2) (yield: 94 8%, IV 14 201024336 was 0.76, Td: 336 ° C). Synthesis Example 3 15.215 g (0.1 mol) of 3,5-diaminobenzoic acid and 3.847 g (0.02 mol) of 1,3-bis(3-aminopropyl)_U,3,3-tetraindole Dioxazane (DSI) and 460 g of NMP were placed in a 1 L glass reaction axe and stirred vigorously at room temperature. Add 3,3,4,4-two of 32.22 * g (0.1 mol) of 3,3,4,4-dibenzoyltetradecanoic acid (BTDA) and 31.02 g (〇.1 mol) After phenyl ether tetracarboxylic dianhydride (〇DPA) was stirred for 1 hour in the reaction, 29.3 g (0.08 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexapropane was added. (BAFA) was stirred at room temperature for 3 hours. Then, 90 g of toluene was added, and the temperature was raised to 150 ° C for 24 hours to carry out a hydrazine imidization (cyclization) reaction, and a polyimine with an OH group was obtained, and then 5.88 g (0.06 mol) was added. The maleic anhydride was allowed to react for 3 hours at room temperature. Then, the resin was poured into a large amount of methanol to obtain 111.3 g of a polyimine polymer (ρι_3) (yield 32.3%, IV: 0.67, Td: 335 ° C). Comparative Synthesis Example 1 41. 5 g (0.1 mol) of 2,2,-diaminophenoxy]phenyl)propane (BAPP) and 9.14 g (0.06 mol) of 3,5-diamino group Benzoic acid (DABZ) and 350 grams of NMP were placed in a 1 L glass reaction axe and stirred vigorously at room temperature. After adding 88.84 g (0.2 mol) of 2,2,-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride oxime (6FDA) in the reaction for 1 hour, add 8.43 g (0.039 mol). 3,3,- • Di-based 4,4'-diamino-biphenyl (HAP) of the ear) was stirred at room temperature for 3 hours. Then, 50 g of stomach toluene was added, and the temperature was raised to 150 ° C for 24 hours, and then the resin was poured into a large amount of methanol to precipitate, thereby obtaining 137.3 g of a polyimine polymer (yield: 93.1%, iv was ο.”, Td: 343. Hey.

The reactants, amounts thereof and physical data of the above synthesis examples and comparative examples are summarized in the following Synthesis Example 1 (PI-1)

BAPP (Mole) (U Synthesis Example 2 Synthesis Example 3 Comparative Synthesis Example (ΡΙ-2) (ΡΙ-3) 1(ΡΙ-〇15 201024336 DABZ(莫耳) 0.06 0.1 0.1 0.06 ΗΑΡ (mole) 0.039 0.098 0.039 BAFA (mole) 0.08 6FDA (mole) 0.2 0.1 0.2 BTDA (mole) 0.1 0.1 ODPA (mole) 0.1 ΜΑ (mole) 0.04 0.098 0.06 DSI 0.02 IV (intrinsic viscosity) 0.81 0.76 0.67 0.79 Td (95% C°〇340 336 335 343 Production Example 1 Photolithographic Protective Film (Coverlay) 20 g of PI4, 0.8 g of IR651 (photopolymerization initiator), and 7.2 g of ethylene glycol diacrylate (M- 1) and 2.8 g of trishydroxyethylpropane trimethacrylate (M-2) 'dissolved in i24 g of NMP' and spoiled at room temperature for 3 hours to obtain a photosensitive gel (V-1). The silicone was coated on polyethylene terephthalate (PET) using a squeegee coating (gap = 100 μτη) and baked at 9 (TC/13 minutes. The enamel film after baking was turned The press is pressed with a copper drop at 120 C and a pressure of 1 kgfcm. This laminate has a desired mask with a UV-exposure device (model ORC-OB-IOOO, 〇rc • MANUFACTRUING) CO. Manufacturing) Exposure (500mJ/cm2) with 1 wt%

The NafO3 aqueous solution was developed for 2 minutes, and then immersed in pure water to wash. Then at 100 ° C / 1 hour, 150 ° C / 1 hour, 200 ° C / 1 hour, 250. (: /2 hours for baking. The pattern of the resolved/closed 100/1 squeak can be obtained by observing the obtained resist pattern by a magnifying glass and an electron scanning microscope. Solubility test: The obtained polyimine is washed and cast into Membrane, the size of 9 * 5.5cm2 dissolved in 1 ml of lwt% NasCO3 aqueous solution, completely dissolved in 2 minutes, expressed as "good" solubility, if more than 2 minutes still left undissolved, it means For the solubility „= 佳” 〇16 201024336 Manufacture of the photosensitive resist film of the production example 2 20 g of PI-2, 0.75 g of IR907 (Ciba Kaki special chemical name, 2_methyl-l-[ 4_(methylthio)phenyl])_2_morpholinyl-propionium), 〇15 ITX (2-isopropyl sputum), 6 g of ethylene glycol diacrylate (10) 丨) and 3 Ethyl ethyl propyl trimethacrylate (M-2), 2.5 g of pentaerythritol diester = ester (M-3) dissolved in 130 g of NMP, and found at room temperature after 3 *. Silkworm = ΓΓΓ ). Preparation of protective film and solubility test of Na2C〇3 aqueous solution = Preparation of photosensitive resist film of Production Example 3 20 g of M-3, 0.53 g of IR907, 0.2 g of ITX, and 3.5 g of B-alcohol diacrylate (10) 1) and 3.4 g of pentaerythritol diacrylic acid g (Μ·3) and gram of isocyanuric acid tris(ethene acrylate) dissolved in 119 g of hydrazine in _4) and mixed at room temperature 3 After a few hours, a photosensitive silicone (γ_3) is obtained. The production of the protective film and the solubility test of the aqueous solution of Na2C〇3 were the same as in Production Example 1. Comparative Production Example 1 Photoresist Protective Film Manufactured 20 g = PI-C, 0.8 g of melon 651 (2,2-dimethoxy phenyl acetophenone), 7.2 g of ethylene glycol diacrylate and 28 g of trishydroxyethylpropane trimethyl propylene, Ss(M-2)' was dissolved in 124 g of NMP' and stirred at room temperature for 3 hours to obtain a photosensitive gel (VC). The production of the protective film and the dissolution of the Na2C03 aqueous solution were the same as in Production Example 1. • The ratio of the photosensitive resist protection 以及 and the solubility test results are shown in the following table 2 ° Table 2 Composition (g) Manufacturing Example 1 Manufacturing Example 2 Manufacturing Example 3 Comparative Manufacturing Resin _ IR651 IR907 (V-1) --乂- --- -^±(100) 4.0 —---_ Suspension _ PI-2 (100) 3.75 (V-3) PI-3 (100) 2.65 1CV-C) PI-C (100) 4.0 ITX 0.75 1.0 M-1 36.0 --- 30.0 17.5 36.0 17 201024336 M-2 14.0 17.5 14.0 M-3 12.5 17.0 M-4 10.5 Resolution 100/100μπι 80/100μπι 100/100μπι 200/250um Film thickness reduction rate (%) "Approx. 11% about 7% about 80/〇 about 10% dissolution in Na2C03 aqueous solution A__ Jiajiajia is not good

It has a photosensitive functional group on the listener I and has an acid group, so it has excellent solubility for an aqueous solution. In addition, since the photosensitive functional group is directly bonded to the polymer main chain, & has a higher Td 'after exposure and development, and does not cause film due to baking, [simplified description of the drawing] [Major component symbol description] % 18

Claims (1)

201024336 VII. Patent application scope: 1. A water-soluble photosensitive polyimide polymer characterized by having the repeating unit of the following formula (I): ΟΑ VMO R ΟΑ γο ΐΝο.. fo-rL—o oa-vno η R 广 J ΟΛ γο - Ν X 9 RX γο Ν ΐ R4 a οh3jh3 cis-lc 53Η53 R9 "ORy——ORg- or m [wherein & is a tetravalent organic group containing 4 or more carbon atoms; & is a trivalent; tetravalent organic group, which may optionally have a carboxyl group; and a horse represents a 2 to 4 valence base. : A represents 〇H or COOH group; R4 and r5 may be the same or different, j) = is shown as a thiol group having 1 to 6 carbon atoms, containing 6 to 2 () carbon atoms and groups, and stretching , aryl aryl wire; R? and Marco can be the same or not the only one is selected from hydrogen, dentate, age, linear or ring containing MO carbon, aryl, fragrant Base and Dickey; private means argon shoulders H1 to 6 carbon atoms of the yard; x means an integer of 1 or 2; y shoulder and k矣Λ2 integer; a, b and n represent an integer greater than or equal to 1; π 2 may be “= _; and each of the above-mentioned fresh-keeping positions may be a water-soluble photosensitive polyimine polymer of a collision polymerization or a heavy weight, wherein more than 0.20 〇 95 ^ 1 1 〇, _ 〜 3 〇 〇, _ 'the intrinsic viscosity (IV) of the article 3. If the patent application weight loss temperature (called 95%) is higher than 30 叱. The water-soluble ii imine polymer, in which the poly-pyrene filament coating is finely coated Thin for 1G~25μιη with 19 201024336 ❹ y 4. ω-struck with the light weight of the fresh-like supporting _ "polymeric imine ~ Si-Q-Si- ο ο b k C = square V Hci x Rg -CR7 == CRfl- ~ - R9 or ❿ aryloxy fluorenyl; hydrazine and horse may be the same or different = alkyl group having 1 to 6 carbon atoms; X represents 1 or &2; i number 7^ The method comprises the following steps: 20 201024336 (b) The poly-branched acid precursor having a carboxyl group and/or a hydroxyl group in the main chain obtained in the above (a) is heated and cyclized at a temperature of 60 to 20 (TC) to obtain a carboxyl group and/or a hydroxyl group in the main chain. Polyethylenimine; and (c) ring-opening reaction of an acid anhydride in a polyethylenimine having a carboxyl group and/or a hydroxyl functional group in the main chain obtained in the above (b) with a dianhydride of the following formula (II) : Λ r6 p ο (wherein CR^-CR8--, ^^ and equine are the same or different and independently selected from hydrogen, dentate m-ring = aryl group containing 6-20 carbon atoms, ___ unit With a fine acid group _ 5. As in the method of claim 4, m has a fluorenyl group and/or a hydroxy functional group used in the step (8) used in the ruthenium diamine. There are several bases in the fourth paragraph of the patent application and/or replaced by the shoulder diamine used in the second step (8) of the base function! The diamine of the amine-supplemented stomach has a di-lowering group selected from the group consisting of if-oxygen oxy-energy (DSI) and 1,3_bis (4-aminobutyl hydrazine 1,1,3,3-tetra Dioxazolidine propyl)-1,3-dimethyl q 3_di-methyl dimethyl dioxin, 1,3-bis(3-ylyl) mountain sand tetramethyl dimethoate ^^^ Oxygen-to-dosing of bis-(4-aminophenyl)-1,1,3,3-tetramethyl 201024336-based dioxane, 1,3-bis(3-aminobenzene) Oxymethyl)-1,1,3,3-tetramethyldiazepine and 1,3-bis(4-aminophenoxymethyl)-ij,3,3-tetramethyl At least one of the group consisting of oxy-combustion. 9. A soluble photosensitive polyimide resin composition comprising (A) a water-soluble unit having the repeating unit of the formula (I) as in the first aspect of the patent application; a photosensitive photopolymerization compound; (9) (f-based) acrylic acid monomer diluent; and (C) a photoinitiator; wherein * component (A): component (8) is in a weight ratio of 100 : 10~ 200, and into eight & light with the composition (A) as 100% by weight, the proportion contained in it "~15 〇 〇 〇 22 201024336 Fourth, the designated representative map: (a) the case specified The table is: ( ). (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: R6 9 o -/ II 6 ii 1 olc· —R—c:—o NHc ΟΛ Yo — . R 广 J OA Yo N 8 R c-R7 c ΟΛ Vo R ΟΠΑ vno N Seven R3—AV - N OA^Vno ΟΛ Yo NN ao H3JH3 c—sIc R H3/ ^v h3 cIsIc k Jb X K9 or 3