TWI376395B - Water soluble photo-sensitive polyimide polymer, process for preparing the same, and photoresist composition containing the same - Google Patents

Description

1376395 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 producing the same. In particular, it relates to a water-soluble photosensitive polyimide polymer which has good solubility to organic solvents and aqueous solutions, and has excellent heat resistance, winding properties and electrical insulating properties after film formation, and can be widely used in electronics. industry. [Prior Art] In the semiconductor manufacturing process, the circuit edge is formed on the substrate by photolithography and silver engraving technology. It is necessary to use the photolithography in the lithography etching process; ^Rouge, the radiation is irradiated by the photosensitive resin The photosensitive property can be obtained by washing the exposed portion or the unexposed portion with a test solution or the like after being exposed through a mask having a desired pattern to obtain a printed circuit board having a desired pattern. The 5587275 patent discloses a polyimine precursor having the following structural unit: 八f ί Π Photosensitive resin used in photolithography etching technology has been developed as in US 5587275 The barrier is made by digging s. _. • HOir r ο ο

Wherein R is a halogen atom or a fluorenyl group.

Thereafter, it is further reacted with a tetrabasic dianhydride monomer 1376395 to obtain a polyimine precursor of the above formula (1). ^ In addition to US6025113, it is disclosed that the polyimine precursor having the formula: (4) is repeated: • 1 J1~~CONH-R2. (°〇〇R3) 2 in

Wherein R1 is a trivalent fine-valent organic group having a tetravalent H-group ring having 4 or more carbon atoms; R3 is at least - and η is 1 or 2; and an organic group is an acidic monovalent group; 〇〇1 - R1 - C0 (000113) 2 (4) Naji base; ΐ f base and ^ proline acid form vinegar bond =;, sub-function "; = and completed the invention. After light development 'Reuse of high-temperature cyclization to form a photosensitive polyfluorene having water solubility. [Inventive content] A quinone imine resin, which is a water-soluble photosensitive poly- conjugate having the formula

Γ—s f oa^vho R OA Yoim 3 y ria^ N OA vno R oanyo En , 2"o N-R/ol?= onu^ VMO Rr OA Yo N ο H3 S3丨 rCH3 1376395

Rg -CRt=cR〇

R9 or

a tetravalent organic group having 4 or more carbon atoms; & is a trivalent or 4 fluorene group, which has a filament on a visual condition; R3 represents an alkyl group of ttt ^ 3 i to 6 carbon atoms, and contains 6 to 2〇m? base: alkyl; ... and heart can be the same or different and stand:

The atomic age is ====== \ and n is 7^ at or equal to 1 integer; m and k are integers greater than ]]; and each of the above repeating units may be block polymerization or random polymerization. The water-soluble photosensitive polyimine polymer of the present invention is converted into polystyrene by weight average/sub-quantity (10) = 〇~qing (8), preferably about 20, _~150, _, The intrinsic viscosity (IV) 2 is 0.20495', preferably _~0.85, and its 5% thermogravimetric loss is less than 350 ° C, preferably less than 340. (:. M cuw/o))

This is a fortune, the characteristic viscosity is determined by using a capillary viscometer (Ubbelohode viscometer) as a solvent for the polymer concentration Q ^ solution [using Ν-methyl ketone ketone] and then calculated by the following formula Its intrinsic cohesive yield = value: ', V inh = ln(t / t0) / 0.5 (g / dl) Re-analyzer t (H) through the viscometer up and down two scales of the blank group time (seconds) t = The time (seconds) in which the polymer solution passes through the upper and lower scales of the viscometer. In the present invention, the above 5% thermal decomposition temperature (1 (1: 95 〇 / (^) is determined by thermal decomposition (TGA) of the resin 5% thermal decomposition The temperature of the water-soluble photosensitive polyimine polymer of the present invention is excellent in the water solubility of the coating. When the film is formed into a film (film thickness: 1 〇 to 25 μm), the film (size: 9*5 5 is dissolved) The dissolution time of the iwto/"sodium carbonate aqueous solution in the loo shoji is less than 2 minutes 1376395 minutes, showing good solubility in the aqueous solution. The light parent is prepared to have the water solubility of the repeating unit of the following formula 1.

Oa^vnoOA Yo N —c=丨Re—

OA^yno OA Yo N

3 y RIA

ΟΛ Vo R OA Yo N oh3jh3 cIs—c Η3/^ν H3 cIsIc cIo

R6= ~~-CR7=CR8 * ίί: ' Rl is a tetravalent organic group containing 4 or more carbon atoms; & is a 3 or 4 base ', and it can be represented by a county with a price of 2 to 4 organic The human surface is not 0H or COOH group; the crucible and the ruler 5 may be the same or different, and are respectively represented by: an alkyl group of 1 to 6 f atoms, an extended aryl group containing fluorene to 20 carbon atoms, and an extension. Alkyl, an extended aromatic alkyl group; R<7 and equine may be the same or different and independently selected from the group consisting of a gas, a halogen, a certain group, a linear or cyclic alkyl group containing UO carbons, and having 6 to 2 carbon atoms. An aryl group, an alkylaryl group and an aralkyl group; R? represents a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms; X represents an integer of 1 or 2; y represents an integer of 0, 丨 or 2; a, b And η represents an integer greater than or equal to 1, m and an integer greater than 〇], wherein each repeat is a block polymerization or a random polymerization; 〃 The method comprises the following steps: (a), four The acid monoanhydride is reacted with a diamine having a slow-acting group and/or a trans-functional group to obtain a poly-proline precursor having a carboxyl group and/or a hydroxyl group in the main chain; wherein the tetrabasic acid-anhydride is a diamine Moer Ratio for the tetracarboxylic dianhydride: two workers: 0.8~1: 1.2. (b) heating and cyclizing the polyproline precursor having a carboxyl group and/or a hydroxyl group in the main chain obtained in the above (a) to obtain a carboxyl group and/or a hydroxyl group having 1376395 polyimine in the main chain; And (ii) subjecting the hydroxyl group of the polyimine having a carboxyl group and/or a hydroxyl functional group in the main chain obtained in the above (b) to a dianhydride of the following formula to form an acid anhydride ring opening reaction: Λ Υ ο ( Π) (where R«= r9 'CR^^CRg-

R9 or ^ and RS may be the same or different and independently selected from the group consisting of hydrogen, halogen, slow-base, containing (four) J chain or cyclic base group, aryl group containing 6 2 〇 carbon atoms, aryl group and aromatic appearance Base, horse table is not hydrogen atom or contains! An alkyl group having up to 6 carbon atoms, ♦ a polymer of the formula (1) having a (iv) acid group on the monolithic domain. ~^Inventive method towel 'The above-mentioned step (8) has a lining and/or a kiln^================================================================================= amine. In the case of using only the first crop of the crop, the Kelin ship-type attachment only indicates the U early position, and the value of the melon can be controlled by controlling the content of the dianhydride (π), for example, -s_n) equivalent to the equivalent amount When m becomes Q, the reduction is equivalent to ί 'gong Chengshe in G. Yu Guan has the secret of reduction. 'The above-mentioned pass_A can be used to indicate 0H and C_.) When the base is equal, m becomes 0, and when the hydroxyl equivalent is greater than the diacid-containing equivalent, 'm becomes Greater than 〇. & 3 The diamine having a residual functional group is the following diamine: 1376395 ch3 ch3 H2N—(03⁄43⁄4—Si—0—Si—(CH2)3—NH2, ch3 ch3 ch3 ch3 H2N—(CH2) 4-Si-Ο-Si-(CH2)4-NH2, II ch3 ch3 ch3 ch3 H2N—(CH2>j—Si—0—Si—(CHi)3—NH2, (1) (2) (3)

CeHs CeHj

Yang k factory IP (6) and f13 f13 r=\ 0CHr?iO-Si-ai2o—/ \ . U L, \_/~f

In the method of the present invention, the above steps (the diamine of the paste, (7) in addition to the above-mentioned diamine having a slow base and/or a base group, and having a reduction of the reaction amount of Pressurized at room temperature 6_t;, preferably in the cyclization reaction in the energy base: the amine can have a carboxyl group and 'or a hydroxyl group, the difference between the two of the beans. The substitution of the diamine of the base may be carried out, but it is preferred that the amine having a nonoxylamine functional group is 5 to 60 mol%, more preferably 10 to 40 mol%, more preferably Na's polyimidate polymer can be used as a photoresist, and it can be used as a photoresist for two coatings on silk, for example, on a woven board, and after 彡, after recognizing the light, the film thickness is reduced due to baking. Moreover, the polyimine polymer of the present invention has a higher ^Td (9 μ, Λ invention and a related sensitizing acid imide tree) because of the sensibility, the g-energy group is directly attached to the polymer main chain. a composition comprising a repeating unit of a water-soluble light-light amine polymer; (8) a (meth)acrylic acid monomer diluent; and (6) a photoinitiator. wherein the component (4) is a knife (B) ratio For example, 1〇〇: 1〇~200, preferably 1〇〇: 4〇~1〇〇. Ingredients (〇^光 initiator, when the component (4) is (10)% by weight, the ratio is aw5 〇 Heavy summer % ' is preferably 1.0 to 5.0 weight 〇 / 〇. [Embodiment] - The method for preparing the brewed imine in the present invention (8) The fourth embodiment of the liver is exemplified by (but not limited to) 2,2,·Shuang (H-phenyl) hexa-propylene dianhydride (6FDA), pyromellitic dianhydride (pmda), 4,4,-oxydiphthalic anhydride (ODPA), 3,3 ',4,4'-biphenyltetracarboxylic dianhydride (61>1) VIII), 3,3,,4,4,_benzophenone tetrazoic acid dianhydride (BTDA), extension ethyl four ship Di-anhydride, butyl sulphate, cyclopentane tetracarboxylic dianhydride, 2,2',3,3,-benzophenone tetracarboxylic dianhydride, 2,2,,3,3,_ Two needles of benzenetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, bis-carboxylphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl) Ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenium anhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl) Terpinear dianhydride, bis(3,4-dicarboxyphenyl)methanhydride, 4,4, _( Two needles of p-phenylenedioxy)dicarbonate, 4,4'·(m-phenyldioxy)diphthalic acid dianhydride, 2,3,6,7-caitetracarboxylic acid dihepatic, 1,4 ,5,8-naphthalene tetraacid, wild, l, 2,5,6-naphthalene tetraphthalic acid dianhydride, iota, 2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10- Perylene tetracarboxylic dianhydride, 2,3,6,7-nonanetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, etc. These dianhydrides may be used alone or It is preferably used in a mixture of plural kinds. Among them, examples of the diamine having a carboxyl group and/or a hydroxyl functional group used in the step (8) of the method for producing a polyimine in the present invention are, for example, but not limited to, for example, 3,5. _Diamine 1376395 Benzoic acid (DABZ), 3,3, _difilament _4,4'-di-biphenyl. The method used in the step (8) of the sulphate imine has the sulphur-oxygen oxime, bismuth (3-aminophenoxymethyl), 3,3-tetrazyloxylated t-double (4- Aminophenoxy, yl)-1, 3,3-tetradecyl oxalate, etc., in the method step (a) of the US and/or brewing imine, in addition to the above-mentioned carboxyamine and ϋ ί ί ί ί ϊ 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基 苯基(TPE_R), 2,: double-rolled base) Ben (APB), 4,4'-bis (4-aminophenoxy) 33, _- ίί3, its it f phenoxy) phenyl] , 2,2-bis[4-(3-amine basic oxy)benyl]propane, 2,2'-bis[4-(3-aminophenoxy)phenyl]butane, 2 [4- (3-aminophenoxy)phenyl]_u mountain 3,3,3_hexapropene, 4 4 phenyl)biphenyl, bis[4_(3·aminophenoxy)phenyl]one , double sulphur test, bis [4_(3 aminophenylphenylphenyl), bis[4_(3-amino-3-phenoxy)benzene fine, etc. The above bisamine can be used alone to make the preparation of the present invention. In the imine method step (8), the diacid reaction can be carried out in an aprotic polar spray, and the non-f subpolar solvent The class is not specific, as long as it does not react with the reactants and products. Specific examples may be 2, Ν-dimethylacetamide (DMAc), N_mercaptopyrrolidone _), N, N_: 2' _F), tetrahydrofuran (THF), dioxane, chloroform (CH 2 N. ton fine _ and secret dimethyl ethene according to the invention (4) method of imine (4) (species, the bis and diamine 11 1376395 reaction Generally, it is carried out at a temperature ranging from room temperature to 90 ° C, preferably from 30 to 75 ° C. In the method for preparing a polyimine of the present invention, in the step (c), the diacid liver can be exemplified by maleic anhydride. Substituted maleic anhydride, tetrahydrophthalic anhydride, surface-substituted tetrahydrophthalic anhydride, methyl phthalic anhydride, by: stearic anhydride, etc. In the composition of the photosensitive light-polyimine resin, the component of the methacrylic acid monomer diluent (in addition to its function as a diluent, since the molecule contains an ethylene functional group, it also contributes to hardening of the composition after illumination). Examples thereof include, for example, ethylene glycol diacrylate, propylene glycol diacrylate, butanediol dipropionate, diethylene glycol diacrylate. Dipropylene glycol diacrylate, trihydroxy methacrylate, triacetic acid vinegar, triethyl ethion triacetate, pentaerythritol, dipentaerythritol tripropylene, ethylene glycol dimethyl propylene: Propylene coffee, butanediol dimercaptopropion, diethylene glycol dimethyl acrylate 酉 曰 一: propylene glycol dimethyl propylene acid g, trisyl propyl trimethyl acrylate vinegar乙乙乙乙烧三曱基丙骑 g, penta dimethyl propyl acrylate, dipentaerythritol dimethacrylate vinegar, etc., the invention of the polyimide resin can be prepared as a photoresist There is a light start 调. The light used in the formulated photoresist composition of the present invention == external light, electron beam, and xenon radiation, etc., and the structure is cleaved to generate an active site such as a radical, a cation or an anion, and A polymerization reaction is carried out by polymerizing a polyimide and an acrylate monomer. Examples of the photoinitiator can be, for example, a butterfly such as 2,2, bis(2-chlorophenyl ° & ethoxylated decyl hydrazino, 2'·dimiso, 2,2, _bis (2) _ desert phenyl)-4:4,:5:5,-肆(·ethoxycarbonylphenyl)_1,2,_diimidazole, 2 2,_double Q 4 -stupid | base m,4', 5,5,-四笨基_u,_ 二味α坐,2,2,_' double^ 2,2'-double (2,4,6·三漠phenyl M,4',5,5 , -tetraphenyl octagonal = for example, triphenylphosphine oxide _, can be said from 雠 △ ), such as bis (2,4,6-trimethylbenzylidene phenyl) phenyl phosphine oxide (4) Hid 81, 12 1376395 (IR819) 'purchased from Ciba Geigy Co., Ltd.; alkyl phenyl ketones, such as hydroxycyclohexyl phenyl ketone [as purchased from Ciba Geigy Inc. in Irgacure 184 (IR184)], 2-曱The base-(4-mercaptophenyl)-2-n-lin-1-propene-j is obtained from Ciba Geigy Co., Ltd. as 907 (JR907). Further examples of the photoinitiator include, for example, a benzoin-based photoinitiator such as a stupid couple, a benzoin methyl ether, a benzoin ethyl ether, a benzoin isopropyl ether, and a stupid Occasionally isobutyl ether, methyl-2-benzylidene benzoate, and the like, and similar derivatives thereof.

Further examples of the photoinitiator include, for example, an acetophenone-based structure such as 2,2-dimethoxy-2-phenylacetophenone [e.g., from Ciba Geigy Co., Ltd. using lrgacure 651 (IR651)] -2-mercapto-1-phenylpropane-1, μ(4.isopropylphenyl)_2-hydroxy-2-methylpropan-1-one, 4-hydrazine hydroxyethoxy) stupyl _ (2-hydroxy-2-propenyl) ketone, 2,2-dimethoxyphenylethylidene, 2,2-diethoxyphenylethylidene, 2-phenylidene-2-diaminoamine- (4_morpholinylphenyl) y-l-ketone, 2,2'-dimethoxyoxyindole, 2,diphenylethyl fluorene, 4-azidoacetophenone, 4 g nitrogen Sub > Basic and similar derivatives. Further examples of the photoinitiator include, for example, benzophenones such as benzophenone, 4,4, bis(diamido)benzophenone, 4,4'-bis(diethylamino)di Phenyl ketone, 3,3, dimethyl 4-methyl benzophenone, and the like. Further examples of the photoinitiator include, for example, a photoinitiator having a diketone structure, for example

Diethyl phthalic acid §, diphenyl cap base ester, mercaptobenzoyl phthalic acid vinegar, and the like; and a photoinitiator having a polynuclear fluorene structure such as hydrazine, 2_ethyl hydrazine 2_ third U Kun 1,4 Qin brewing and similar derivatives; seven classes & sister also (10) e) structure of light initiator such as (four) ketone, 嗟 _, 2, 4 _ diethyl ketone 2_Chlorobenzamine and the like; a photoinitiator having a diazo structure such as 4_diazodiphenylamine, 4_diazo _4, _ ί ϋΪΪ, 4 _ Wei Ke Shi methoxy Phenylamine and the like and similar derivatives; and, photoinitiator of n such as 2_(2,_吱-mercaptoethylidene)_4,6_bis (trisole gas)>4,6 · bis (trisyl)-s-triazine such as (tetra)yl >s three., 2_(2, prepared 4, _methylphenyl)-, x (_chloromethyl) s • triterpene,... .synylene, ethyl 4,6-bis (trisole 13 1376395)-s-triazine, and the like. These photoinitiators may be used alone or in combination of two or more. When the component (A) is 1% by weight, the photoinitiator (C) is used in an amount of 〇丨 15 15 % by weight, preferably 1.0 to 5.0% by weight. The following Synthesis Example will be further detailed description and examples, but the

The present invention is intended to be illustrative only and not to limit the scope of the invention. X Synthesis Example 1 41.05 g (0.1 mol) of 2,2,_bis-[4-(4-aminophenoxy)phenyl]propane (BAPP) and 9.14 g (0.06 mol) of 3, 5-Diaminobenzoic acid (DABZ) and 350 g of N-methylindole (N)y[p) were placed in a 1 liter glass reaction flask and vigorously incubated at room temperature. Add 88.48 g (0.2 mol) of 2,2,·bis(3,4-dicarboxyphenyl)hexafluoropropanone (6FDA) in the reaction flask for 1 hour, then add 8.43 g (0.039). f, 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 (Malaysia of 〇.〇4) The reaction was continued for 3 hours at room temperature. Then the resin was poured into a large amount of methanol to obtain 136.2 g of a polyimine polymer (pI-1) (yield: 90.01%, IV was 0.81). , Td (95%): 340. 合成. Synthesis Example 2 15.215 g (〇·ΐ莫耳) of 3,5-diaminobenzoic acid (DABZ) and 200 g

Place the crucible into the glass reaction axe of il' vigorously stirring at room temperature. Add 4442 g (0.1 mol) of 2,2'-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and 32.22 g (〇.1 mol) of 3,3,4 , 4-benzophenone tetracarboxylic dianhydride (BTDA), after reacting for 1 hour, add 21.19 g (0.098 mol) of 3,3,-dihydroxylamine group at room temperature Stir for 3 hours. Then, 3 gram of terpene is added, and the reaction is carried out at a temperature of 15 〇〇c for 24 hours to carry out a hydrazine imidization (cyclization) reaction, thereby obtaining a polyimine with an OH group, and then adding 5 88 g. The maleic anhydride of (〇〇6 mol) was further reacted at room temperature for 3 hours. Then, the resin was poured into a large amount of methanol to obtain 112.7 g of a polyimine polymer (2) (yield: 94.83⁄4, IV 14 1376395 / 0.76, Td: 336 ° C). Synthesis Example 3 15.215 g (G.1 mol) of 3,5·diaminobenzoic acid and 3 g of g (G G2 1,3-bis(3-aminopropyl;)-1,1 , 3,3-tetradecyldioxane (〇; 51) and 46 g of NMP were placed in a 1 L glass reaction axe and stirred vigorously at room temperature. 32 22 g (0.1 mol) was added. 3,3,4,4-benzophenone tetracarboxylic acid dianhydride 3,3,4,4-diphenyl ether tetracarboxylic dianhydride of 10,000 and 3 j 〇 2 g (formerly molar) (〇DPA) After stirring for a few hours in the reaction, 'Additional 29.3 g (0.08 mol) of 2,2·bis(3-amino-4-yl-phenylphenyl)hexafluoropropane (BAFA) was added at room temperature. The mixture was stirred for 3 hours. Then, gram of toluene was added, and the temperature was raised to 150 ° C for 24 hours to carry out the oxime imidization (cyclization) reaction, and the poly-imine with ? 0 group was obtained, and then 5.88 g was added. The maleic anhydride (0.06 mol) was further reacted at room temperature for 3 hours, and then the resin was poured into a large amount of methanol to precipitate 111.3 g of a polyimine polymer (3) (yield: 92). 3%, Iv is 〇67, Td: 335〇C). Comparative Synthesis Example 1 * 41.05 g (0.1 mol) of 2,2,-bis-(4-[4-aminophenoxy]phenyl)propane (BAPP) and 9.14 g (〇.〇6 Mo The ear 3,5-diaminobenzoic acid (9)^) and 35 g of NMP were placed in a 1 L glass reaction axe and stirred vigorously at room temperature. Add 88.84 g (0-2 mol) of 2,2,_bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and stir for 1 hour in the reaction, then add 8 43 g (0.039 mo) The 3,3,-dihydroxy-4,4'-diaminobiphenyl (hap) of the ear was stirred at room temperature for 3 hours. Then, 50 g of f benzene of the stomach was added to increase the temperature until the reaction was carried out for 24 hours, and the petrolatum was poured into a large methanol to precipitate, and 137.3 g of a polyimine polymer (pj_c) was obtained (yield: 93.1). % 'IV is 0.79, Td: 343. 〇.

The reactants, amounts and physical data of the above synthesis examples and comparative examples are summarized in the following Synthesis Example 1 (H-1) Synthesis Example 2 (PI-2) Synthesis Example 3 (PI-3) Comparative Synthesis Example 1 (PI- C) BAPP (Mole) 0.1 0.1 15 1376395 DABZ (Mohr) 0.06 0.1 0.1 0.06 HAP (Mohr) 0.039 0.098 0.039 BAFA (Moule) 0.08 6FDA (Mohr) 0.2 0.1 0.2 BTDA (Mole) 0.1 0.1 ODPA (mole) 0.1 MA (mole) 0.04 0.098 0.06 DSI 0.02 IV (intrinsic viscosity) 0.81 0.76 0.67 0.79 Td (95%) (°C) 340 336 335 343 Production Example 1 Photomask Protective Film (Coverlay) 2 g of PI-Bu 0. 8 g of IR651 (photopolymerization initiator), 7.2 g of ethylene glycol diacrylate (M-1) and 2.8 g of trishydroxyethylpropane trimethacrylate ( M-2), dissolved in I24g of NMP, and stirred at room temperature for 3 hours, then the photosensitive gelatin (V-1) was obtained. The silicone was coated on polyethylene terephthalate (PET) using a squeegee coating (gap = 1 〇〇 μηη): and at 90. (:/13 minutes baking. The baked film was pressed on a transfer machine at 120 ° C and a pressure of 1 kgfcm. The laminate was required.

The pattern is exposed to a light-shielding device (model 〇RC_〇B_1〇〇〇, manufactured by 〇RC MANUPACTRUINGCO.) for exposure (500 mJ/cm2), and i is added with %

The Na2C03 aqueous solution was developed for 2 minutes, and then immersed in pure water for HKTC/1 hour, 150 〇C/1 hour, 2 〇 (TC/1 hour, for 2 hours). The light was observed by a magnifying glass and an electron scanning microscope. Resistance pattern, densely lined with 100/10〇Mm. (4) Γ 到 to analysis / Solubility test: The obtained polythene imide is washed into tungsten, taking the size of 9*55 coffee 2 dissolved in Jiayou for more than 2 minutes still left In the case of undissolved matter, it is expressed as solubility. It is not 1376395. In the case of the production of the photoreceptor protective film of the example 2, the 口=ΛΥ=α75g of the 1^7 (Cibajiaji Chemicals Co., Ltd., two), 6 Gb ethylene glycol dipropyl axis 2 3 =, hydroxyethyl propane trimethacrylate '25 g of pentaerythritol ^ 3) dissolved in 13 〇 g of nmp, and disturbed at room temperature 3 * After the time = ΓΓ: 2). Lai's age, attitude, and tempering degree

20 grams of PI-3, 0.53 grams of IR907, 0.2 grams of bismuth, 3.5 grams of ethylene glycol dipropylene, ester (Μ-1) and 3.4 grams of pentaerythritol dipropylene vinegar _) and gram Isocyanuric acid di(ethyryl citrate) (Μ-4) was dissolved in 119 g of jsj]y[p, and stirred at room temperature for 3 hours to obtain a photosensitive PI gel (¥3). . The production of the protective film and the solubility test of the aqueous solution of NafO3 were the same as in Production Example 1. Comparative Production Example 1 Photoresist Protective Film Manufactured 20 g of PI-C, 0.8 g of 111651 (2,2-dimethoxy-2-phenylacetophenone), and 7.2 g of ethylene glycol diacrylate The ester (M4) and 28 g of trishydroxyethylpropane trimethacrylate (M-2) were dissolved in 124 g of NMP and stirred at room temperature for 3 hours to obtain a photosensitive PI gel (VC). The production of the protective film and the solubility test of the aqueous solution of Na2C03 were the same as in Production Example 1. The ratio of the photosensitive resist protective film and the solubility test results are shown in the following table 2 ° Table 2 Composition (g) Manufacturing Example 1 (V-1) Manufacturing Example 2 (V-2) Manufacturing Example 3 (V-3) Comparative Manufacturing Example 1 (VC) Resin PI-1 (100) PI-2 (100) PI-3 (100) PI-C (100) IR651 4.0 4.0 IR907 - 3.75 2.65 ΓΓΧ_ 0.75 1.0 Μ-1 — 36.0 30.0 17.5 36.0 17 1376395 M-2 M-3 M-4 Resolution Film Thickness Reduction Rate (%) Solubility in Na2C03 Aqueous Solution 14.0 17.5 12.5 14.0 100/100μιη Approx. 11% Good 80/100μιη Approx. 7% Good 17.0_ 10.5_ 100/100μιη Approx 8 ° / 〇 good 200 / 250μπι about 10% poor table shows that the first batch of sensory level ^ with the sensation of the ruthenium and has an acid group, so the T-sensitive functional group is directly connected to the polymer backbone After development, it will not be _baked and the film thickness will be seriously reduced: [Main component symbol description]

Claims (1)

Patent Application No. 097151347 Patent Application Substitute Replacement (August 101) Public § Μ 》 》 月 日 修正 修正 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 亚 VII. Patent application scope: 1. A water-soluble photosensitive polyfluorene unit: mRi is a tetravalent organic group containing 4 or more carbon atoms; r2 is a trivalent or 媳i machine base, and it may have a radical on the substrate; R3 represents The valence of 1 to 4 represents 0H or (10) (4): the heart and the ^ may be the same or different, and the fraction # is an alkyl group having 1 to 6 carbon atoms, a base group having 6 to 20 carbon atoms, a aryl group, Aryloxyalkylene; RjR8 may be the same or different = independently selected from hydrogen, relatively, silk, 12 () linear or cyclic (four) carbon atoms of aryl, silk and aromatic filaments; R9 represents hydrogenogen t or a group containing 1 to 6 carbon atoms; X represents an integer of 1 or 2; y represents an integer of 〇1 or 2; a, b and η represent an integer greater than or equal to 1; m represents An integer greater than or equal to each other; and each of the above repeating units may be a block poly s or may be a random polymerization. 1 ' Please refer to the water-soluble photosensitive polyimide polymer of the first item of the patent range, wherein the average molecular weight is 1〇〇〇〇~3(8), and the intrinsic viscosity (IV) is: 0.95 and 5% thereof. The thermogravimetric loss temperature (Td (95%)) is higher than 3 〇 (rc. • The water-soluble photosensitive polyimide polymer according to claim 1 of the patent range, wherein the water-soluble photosensitive polyimide The polymer is coated into a film having a film thickness of 10 to 25 μm. Patent Application No. 097151347 Patent Application No. (August, 2011) = 'Dissolve the film size 9*5.5 cm2 in 1000 ml of a lwt% sodium carbonate aqueous solution The dissolution time is less than 2 minutes. 4. A method for preparing a water-soluble photosensitive polyimine polymer having a repeating unit of the following formula (I), CRp=CR8-, [Formula jt7 is a tetravalent organic group containing 4 or more carbon atoms; r2 is a trivalent or tetravalent organic group, which may optionally have a carboxyl group; a horse represents a divalent to tetravalent organic group; and A represents an OH or COOH group;仏 and R5 may be the same or different, respectively represented as a stretching group having 1 to 6 carbon atoms, an extended aryl group having 6 to 2 carbon atoms, an exoaryl group, and an extended aryloxy group. The base 7 and the core may be the same or different and independently selected from the group consisting of a mouse, a halogen, a group, a linear or cyclic alkyl group having 1 to 20 carbons, an aryl group having 6 to 20 carbon atoms, and an alkyl group. And aralkyl; ^ represents a hydrogen atom or a burnt group having 1 to 6 carbon atoms; X represents an integer of 1 or 2; y represents an integer of 〇, 1 or 2; and a, b and η represent greater than or equal to i An integer; m and k represent an integer greater than or equal to ]]; wherein each repeat sheet may be a block polymerization or a random polymerization; the method includes the following steps: (a) subjecting the tetracarboxylic dianhydride to having a carboxyl group and/or The hydroxy-functional diamine is subjected to a reaction at a temperature of up to 90 C under normal pressure to obtain a melamine group having a sulfhydryl group and/or a B group of a base b group, wherein the tetrabasic acid is The molar ratio of the diamine to the diamine is tetracarboxylic dianhydride: diamine = 1: 0.8~1: 1.2; the patent application scope of the patent application No. 097151347 (August, 2011) (b) The polyproline 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 200 ° C to obtain a carboxyl group and/or a hydroxyl group in the main chain. Polyimine; and (c) subjecting the main chain of the above (b) to a ring-opening reaction of a 35-group of a county- and/or trans-functional aryl imino group to the two sides of the following formula (11) : (II) r9 Rg Or halogen, carboxyl group, containing 1-20 (wherein R6=-CRp=CR8--, R7 and 118 may be the same or different and independently selected from hydrogen m-ton, tm-stone, ortho-ring, including 6 An aryl group of -20 carbon atoms, an aryl group and a fii 9 core or a filament having 1 to 6 carbon atoms; an amine of the formula (1) represents a repeating unit of an acrylic group having an acrylic group. The method of the fourth aspect of the invention, wherein the above-mentioned step (8) and the diamine having a functional group have a functional group of a base and a silk, wherein the above The diamine moiety having a diamine in the step (8) is subjected to the method of the sixth aspect of the dioxane functional group, wherein the diamine having a Wei-burning functional group accounts for 5 to 60 moles of diamine / 0. The method of the first item, wherein the two of the functional groups of the tree sister are ms/, , ! from &, 3·bis (3_aminopropyl)>u, 3,3·tetramethyldish Ethanol and its t-diaminobutyl ^1'1,3,3' tetramethyl bismuth oxylate ' I3-double (3_ ^ 土·ι,3_一曱基_1,3-二Phenyl sulphate, 1,3 bis (3_amine, stupid sputum, 1,3,3·tetradecyl sulphate, u na-aminophenyl A (August 101 '), 1,3_bis(3_aminophenoxymethyl)_u, 3,3_tetramethyl 2: group of oxymethyl groups The composition of the ribonuclear polyimine resin, which comprises (Α) such as the patent compound; the water miscellaneous lack of the imine poly.. (Λ): with the paste Q_ scale, return