JP2010155962A - Water-soluble photosensitive polyimide polymer, method for producing the same, and photoresist composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-soluble photosensitive polyimide polymer, a method for producing the same, and a photoresist composition containing the same. <P>SOLUTION: The water-soluble photosensitive polyimide polymer is produced by the steps of: (a) allowing tetracarboxylic dianhydride to react with a diamine having a carboxyl group and/or a hydroxy functional group to synthesize a polyamide acid precursor having a carboxyl group and/or a hydroxy functional group in the main chain; (b) heating and cyclizing the polyamide acid precursor having a carboxyl group and/or a hydroxy functional group in the main chain obtained in the step (a) to synthesize a polyimide having a carboxyl group and/or a hydroxy functional group in the main chain; and (c) allowing a hydroxy group of the polyimide having a carboxyl group and/or a hydroxy functional group in the main chain obtained in the step (b) to react with a dianhydride to subject the dianhydride to ring opening reaction to synthesize a polyimide polymer having an acrylic acid group in the main chain. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a water-soluble photosensitive polyimide polymer and a method for producing the same, and in particular, has high solubility in an organic solvent or an alkaline aqueous solution, and has excellent heat resistance, flexibility, and electrical insulating properties after film formation, and is widely used in the electronic industry. The present invention relates to an applied water-soluble photosensitive polyimide polymer.

In semiconductor manufacturing processes, circuit patterns are created on a substrate by photolithography / etching technology, but when using photolithography / etching technology, photosensitive resin is indispensable, and photosensitive resin against light radiation Through exposure to light, a photomask on which a predetermined pattern is formed is exposed, and an exposed portion or an unexposed portion is developed with an alkaline solution or the like to form a predetermined pattern on a printed board.
Photosensitive resins used in photolithography and etching techniques have been considerably developed. For example, a polyimide precursor posted in US Pat. No. 5,587,275 has a structure represented by the following formula (1):

X represents a tetravalent organic group of an aromatic ring, Y represents a divalent organic group of an aromatic ring or a divalent organic group of a siloxane bond, and Z represents a hydrogen atom or the following formula (2) It contains an acryloxy group or a methacryloxy group,

R is a hydrogen atom or a methyl group.
In US Pat. No. 5,587,275, a diamine and (meth) acrylic acid glycidyl ether are reacted to obtain a diamine monomer having an acryloxy group, and then a tetracarboxylic dianhydride monomer is further reacted to form the above formula (1 ) A polyimide precursor is obtained.
Further, in US Pat. No. 6,025,113, a polyimide precursor having an overlapping structure represented by the following formula (3) and formula (4) is posted,

In US Pat. No. 6,025,113, in order to increase the photosensitivity of a photoresist, an ester bond is formed between an acrylic group and a polyamic acid, and after exposure / development, a cyclization reaction is performed at a higher temperature, and finally heat resistance is achieved. And polyimide with excellent flexibility.
The inventors have researched and developed a water-soluble photosensitive polyimide resin, studied functional groups of the produced polyimide resin, and completed the present invention.

US Pat. No. 5,587,275 US Pat. No. 6,025,113

An object of this invention is to provide a water-soluble photosensitive polyimide polymer, its manufacturing method, and a soluble photosensitive polyimide resin composition.

Having an overlapping structure of the following formula (I):

Each of the above overlapping structures may be a block copolymer or a random polymer.
The water-soluble photosensitive polyimide polymer of the present invention has a polystyrene-equivalent weight average molecular weight Mw by gel permeation chromatography (GPC) of about 10,000 to 300,000, preferably about 20,000 to 150,000, The intrinsic viscosity (IV) is 0.20 to 0.95, preferably 0.60 to 0.85, and the 5% thermal weight loss temperature (Td (95%)) is 260 ° C. or higher, and 300 ° C. The above is preferable.
In the present invention, the intrinsic viscosity is measured with a capillary viscometer (Nb-methyl-pyrrolidone (NMP) as a solvent) after preparing a polymer concentration in a solution of 0.5 g / dL. Intrinsic viscosity value is calculated,

Among them, t0 = time (seconds) for the solvent to pass through the blanks on the two standard lines above and below the viscometer
t = time (seconds) for the polymer solution to pass the two standard lines above and below the viscometer
In the present invention, the 5% thermal decomposition temperature (Td (95%)) is measured by a thermogravimetric apparatus (TGA) at the time of 5% thermal decomposition of the resin.
The water-soluble photosensitive polyimide polymer of the present invention has good solubility in an alkaline aqueous solution, and when a coating film is formed (film thickness: 10 to 25 μm), the film (dimension: 9 × 5.5 cm ² ) is reduced to 1000 ml of 1 wt% sodium carbonate aqueous solution. It takes only 2 minutes to dissolve, indicating that it is soluble in an alkaline aqueous solution.
The present invention also relates to a method for producing a water-soluble photosensitive polyimide polymer having an overlapping structure represented by the following formula (I):

And each of the above overlapping structures may be a block copolymer or a random polymer,
The method includes the following steps:
(A) by reacting a tetracarboxylic dianhydride with a diamine having a carboxyl group and / or a hydroxy functional group to synthesize a polyamic acid precursor having a carboxyl group and / or a hydroxy functional group in the main chain; In this case, the molar equivalent ratio of tetracarboxylic dianhydride to diamine (tetracarboxylic dianhydride: diamine) is 1: 0.8 to 1: 1.2,
(B) Next, the polyamic acid precursor having a carboxyl group and / or a hydroxy functional group in the main chain obtained in the above (a) is heated and cyclized, so that the main chain has a carboxyl group and / or a hydroxy function. A polyimide having a group,
(C) Further, the hydroxy group of the polyimide having a carboxyl group and / or a hydroxy functional group in the main chain obtained in (b) above and the dianhydride of the following formula (II) are subjected to a ring-opening reaction of the anhydride. ,

A polyimide polymer having an acrylic acid group in the main chain of the overlapping structure represented by the above formula (I) is synthesized.

  In the method of the present invention, the diamine having a carboxyl group and / or a hydroxy functional group used in the step (a) is a diamine having only a carboxyl functional group, a diamine having only a hydroxy functional group, or a hydroxy group and a carboxyl functional group. Although a diamine having a group at the same time may be used, when a diamine containing only a hydroxy group is used as a raw material diamine, A in the above formula (I) shows a polymerization structure of only OH, and dianhydride (II ), The m value can be controlled. For example, when the anhydride equivalent of dianhydride (II) is equal to the hydroxy group equivalent, m is 0 and the hydroxy group equivalent is 2 When greater than the anhydride equivalent weight of anhydride (II), m is greater than 0 and the hydroxy and carboxyl functional groups are When using the diamine that sometimes has, A in the above formula (I) can obtain a polymerized structure of OH and COOH, and the m value can be controlled by controlling the content of dianhydride (II). For example, when the anhydride equivalent of the dianhydride (II) is equal to the hydroxy equivalent, m is 0, and when the hydroxy equivalent is greater than the anhydride equivalent of the dianhydride (II), m is greater than 0. Become.

In the method of the present invention, the diamine having a carboxyl group and / or a hydroxy functional group used in the step (a) may be partially substituted with a diamine having a siloxane functional group.
Examples of the diamine having a siloxane functional group in the present invention include the following diamines.

In the method of the present invention, the diamine used in the step (a) has the performance required for the polyimide resin obtained at the end of the present invention in addition to the diamine having the carboxyl group and / or hydroxy functional group. In the range which does not influence, you may use together the diamine often used for manufacture of a polyimide resin normally.

In the method of the present invention, the condensation reaction in the step (a) is carried out at normal pressure and room temperature to 90 ° C, and among them, 30 to 75 ° C is preferable. The cyclization reaction in the step (b) is performed in the range of 60 to 200 ° C, and preferably 90 to 150 ° C.
In the method of the present invention, the diamine having a carboxyl group and / or a hydroxy functional group in the step (a) may be partially substituted with a siloxane functional group-containing diamine, but the ratio of the two is particularly limited. First, the molar equivalent ratio of tetracarboxylic dianhydride to the total amount of diamine should be within the above range, and the diamine having a siloxane functional group preferably occupies 5 to 60 mol% of the total diamine, more preferably 10 -40 mol%, and most preferably 15-20 wt%.

Although the polyimide polymer of the present invention is used as a photoresist, it is applied to a substrate as a photoresist, for example, after being applied to a copper substrate, after development / exposure, and after exposure, the film is dried. Does not decrease. The polyimide polymer of the present invention has a relatively high Td (95%) because the photosensitive functional group is directly connected to the polymer main chain.
Furthermore, the present invention relates to a soluble photosensitive polyimide resin composition, wherein (A) a water-soluble photosensitive polyimide polymer having an overlapping structure of the above formula (I), (B) a (meth) acrylic acid monomer diluent, and (C ) Containing a photoinitiator, and the weight ratio of component (A): component (B) is 100: 10 to 200, preferably 100: 40 to 100, and with respect to 100% by weight of component (A), The content rate of a component (C) photoinitiator is 0.1-15.0 weight%, and 1.0-5.0 weight% is preferable.

  In the present invention, examples of (but not limited to) tetracarboxylic dianhydrides used in the polyimide production step (a) include, for example, 2,2′-bis (3,4-dicarboxylphenyl). Hexafluoropropane dianhydride (6FDA), pyromellitic dianhydride (PMDA), 4,4'-oxydiphthalic dianhydride (ODPA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride Product (BPDA), 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA), ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride 2,2-bis (3,4-dicarboxylphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxylphenyl) propane dianhydride, bis (3,4-dicarboxylphenyl) ether Anhydride, bis (3,4-dicarboxylphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxylphenyl) ethane dianhydride, bis (2,3-dicarboxylphenyl) methane dianhydride Bis (3,4-dicarboxylphenyl) methane dianhydride, 4,4 '-(p-phenylenedioxy) diphthalic dianhydride, 4,4'-(m-phenylenedioxy) diphthalic acid Anhydride, 2,3,6,7-naphthyltetracarboxylic dianhydride, 1,4,5,8-naphthyltetracarboxylic dianhydride, 1,2,5,6-naphthyltetracarboxylic dianhydride , 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-berylenetetracarboxylic dianhydride, 1,2,7,8-anthracenetetracarboxylic dianhydride And 1,2,7,8-phenanthrenetetracarboxylic dianhydride, etc., and these dianhydrides may be used alone or in combination. Preferably, it is a diamine having a carboxyl group and / or a hydroxy functional group used in the polyimide production step (a) in the present invention, and examples thereof (but not limited thereto) include, for example, 3,5-diamine. Examples include benzoic acid (DABZ), 3,3′-dihydroxy-4,4′-diamine biphenyl.

  Examples of the diamine having a siloxane functional group used in the polyimide production process (a) in the present invention include 1,3-bis (3-aminopropyl) -1,1,3,3-tetra. Methyldisiloxane (DSI), 1,3-bis (4-aminobutyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (3-aminopropyl) -1,3-dimethyl- 1,3-diphenyldisiloxane, 1,3-bis (3-aminophenyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (4-aminophenyl) -1,1,3 , 3-tetramethyldisiloxane, 1,3-bis (3-aminophenoxylmethyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (4-aminophenoxylmethyl) -1 , 1,3 There are 3-tetramethyldisiloxane and the like.

  In the production step (a) of the polyimide in the present invention, the diamine other than the diamine having a carboxyl group and / or the hydroxy functional group and the siloxane functional group is, for example, phenyldiamino (PDA), 4,4′- Oxydianiline (ODA), 1,3-bis (4-aminophenoxy) benzene (TPE-R), 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), bis [4- (4-Aminophenoxy) phenyl] sulfone (BAPS), 1,3-bis (3-aminophenoxy) benzene (APB), 4,4′-bis (4-aminophenoxy) -3,3′-dihydroxydiphenyl ( BAPB), bis [4- (3-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) ) Phenyl] ethane, 1,2-bis [[4- (3-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2′-bis [4 -(3-aminophenoxy) phenyl] butane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfoxide, Examples include bis [4- (3-aminophenoxy) phenyl] sulfone and bis [4- (3-aminophenoxy) phenyl] ether, but the diamine is a simple substance. But also used by several mixed.

In the polyimide production step (a) in the present invention, the reaction between the dianhydride and the diamine is carried out with an aprotic polar solvent, but the kind of the aprotic polar solvent is not particularly limited, and the reactant and the product. If it does not react, it is good. As specific examples (but not limited to), for example, N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), tetrahydrofuran (THF) , Dioxane, chloroform (CHCl ₃ ), dichloromethane and the like, and the use of N-methyl-2-pyrrolidone (NMP) and N, N-dimethylacetamide (DMAc) is preferred.

  In the polyimide production step (a) of the present invention, the reaction between the dianhydride and the diamine is usually performed at room temperature to 90 ° C, and preferably at a temperature in the range of 30 to 75 ° C.

  In the polyimide production step (c) of the present invention, examples of dianhydrides (II) include maleic anhydride substituted with maleic anhydride, tetrahydrophthalic anhydride substituted with tetrahydrophthalic anhydride, and methylene phthalic anhydride. And methylene phthalic anhydride substituted with.

In the soluble photosensitive polyimide resin composition of the present invention, the component (B) (meth) acrylic acid monomer diluent is used as a diluent, and contains an ethylene functional group in its molecule. It also helps to cure the composition. Examples include, for example, ethylene glycol diacrylate, propylene glycol diacrylate, butylene glycol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, trimethylolpropane triacrylate, triethylolpropane triacrylate, pentaerythritol diacrylate, Dipentaerythritol triacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, butylene glycol dimethacrylate, diethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, triethylolpropane trimethacrylate Acrylate, pentaerythritol dimethyl Acrylate, and the like dipentaerythritol trimethacrylate.

  When the polyimide resin of the present invention is prepared into a photoresist, it is prepared as a photoinitiator. The photoinitiator used in the photoresist composition of the present invention is visible light, ultraviolet light, far ultraviolet light, electron beam or X When irradiated with light such as rays, the molecular structure is disrupted to form active sites such as radicals, cations or anions, and a polymerization reaction between polyimide and (meth) acrylate monomer is carried out. Like that.

  Examples of photoinitiators include, for example, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (4-ethoxycarbonylphenyl) -1,2′-di of imidazoles. Imidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetra (4-ethoxycarbonylphenyl) -1,2′-diimidazole, 2,2′-bis (2 , 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-diimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-diimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-diimidazole And 2,2′-bis (2,4,6-tribromo Eniru) -4,4 ', include 5,5'-tetraphenyl-1,2'-diimidazole.

  Examples of photoinitiators include, for example, triphenylphosphine oxide (TPO, commercially available from BASF), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Irgacure 819 (IR819), Ciba Geigy) Alkylphenyl ketones include, for example, 1-hydroxycyclohexyl phenyl ketone [eg, Irgacure 184 (IR184), purchased from Ciba Geigy], 2-methyl- (4-methylthienyl) -2-morpholino-1- Propan-1-one [for example, Irgacure 907 (IR907), purchased from Ciba Geigy, Inc.].

  Further, as examples of photoinitiators, benzoin photoinitiators include, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, methyl-2-benzoyl benzoate, and the like. And the like derivatives.

  Furthermore, as examples of photoinitiators, structural examples of acetophenones include, for example, 2,2-dimethoxy-2-phenylacetophenone [eg, Irgacure 651 (IR651), purchased from Ciba Geigy], 2-hydroxy-2 -Methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2 -Propyl) ketone, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2,2'-dimethoxy -1,2-diphenylethane-1-one, 4-azidoacetophenone, 4-azidobenze Examples include lidene acetophenone and the like derivatives.

  Further, as examples of photoinitiators, benzophenones include, for example, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 3,3′-dimethyl-4-methoxy. Examples include benzophenone and the like derivatives.

  As examples of photoinitiators, examples of photoinitiators having an α-dione structure include diacetate, dibenzoylformate, methylbenzoylformate, and the like derivatives.

  Examples of the photoinitiator having a polynuclear quinone structure include anthraquinone, 2-ethylanthoquinone, 2-tert-butylanthraquinone, 1,4-naphthalenequinone, and the like, and derivatives thereof. Examples of the photoinitiator include xanthone, thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and the like derivatives.

  Photoinitiators having a diazo structure include, for example, 4-diazodiphenylamine, 4-diazo-4′-methoxydiphenylamine, 4-azido-3-methoxydiphenylamine, and the like derivatives, and photoinitiators having a triazine structure. Examples of the initiator include 2- (2′-furanethylidene) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ′, 4′-dimethoxystyrene) -4,6-bis (trichloromethyl). ) -S-triazine, 2- (4'-methoxynaphthalene) -4,6-bis (trichloromethyl) -s-triazine, 2- (2'-bromo-4'-methylphenyl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (2′-thiophenethylidene) -4,6-bis (trichloromethyl) -s-triazine, etc. And derivatives of the kind thereof.

  The photoinitiator may be used alone or in combination of two or more, but the amount of the photoinitiator (C) used is 0.1 to 15.0% by weight relative to 100% by weight of the component (A). And 1.0 to 5.0% by weight is preferable.

  The invention will be described in detail with reference to the following synthesis examples and examples, but these synthesis examples and embodiments are used to illustrate the invention and thereby limit the scope of the invention. It is not a thing.

Synthesis example 1
41.05 g (0.1 mol) of 2,2′-bis- [4- (4-aminophenoxy) phenyl] propane (BAPP), 9.14 g (0.06 mol) of 3,5-diaminobenzoic acid (DABZ) ) And 350 g of N-methyl-2-pyrrolidone (NMP) are placed in 1 L of a glass reaction bottle and stirred vigorously at room temperature, and then 2,2′-bis (3,4-dicarboxylphenyl) hexafluoropropane After adding 88.48 g (0.2 mol) of dianhydride (6FDA) to the above glass reaction bottle and stirring for about 1 hour, 3,3′-dihydroxy-4,4′-diaminobiphenyl ( Add 8.43 g (0.039 mol) of HAP) and stir at room temperature for about 3 hours. Next, 50 g of toluene was added, the temperature was raised to 150 ° C., and an imidization (cyclization) reaction was performed for 24 hours. As a result, a polyimide having an OH group was obtained, and then 3.92 g of maleimide (MA) ( 0.04 mol) was added, and the reaction was continued at room temperature for about 3 hours. Then, the resin was poured into a large amount of methanol to precipitate a polyimide polymer, whereby 136.2 g of polyimide polymer (PI-1) was obtained. (Production rate: 90.01%, IV 0.81, Td (95%): 340 ° C.).

Synthesis example 2
After putting 15.215 g (0.1 mol) of 3,5-diaminobenzoic acid (DABZ) and 200 g of NMP into 1 L of a glass reaction bottle and stirring vigorously at room temperature, 2,2′-bis (3,4- Dicarboxylphenyl) -hexafluoropropane dianhydride (6FDA) 44.42 g (0.1 mol), 3,3,4,4-benzophenonetetracarboxylic dianhydride (BTDA) 32.22 g (0.1 mol) ) And stirring for about 1 hour while reacting, 21.19 g (0.098 mol) of 3,3′-dihydroxy-4,4′-diaminobiphenyl is added and stirred at room temperature for about 3 hours. Next, 30 g of toluene was added, the temperature was raised to 150 ° C., and an imidization (cyclization) reaction was carried out for 24 hours. As a result, a polyimide having one OH group was obtained. After 88 g (0.06 mol) was added and reacted at room temperature for 3 hours, the resin was poured into a large amount of methanol to precipitate the polyimide polymer, thereby obtaining 112.7 g of polyimide polymer (PI-2). (Production rate: 94.8%, IV 0.76, Td: 336 ° C.).

Synthesis example 3
15.215 g (0.1 mol) of 3,5-diaminobenzoic acid, 3.847 g of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane (DSI) (0. 02 mol) and 460 g of NMP in 1 L of a glass reaction bottle, and after vigorously stirring at room temperature, 32.22 g (0.1 mol) of 3,3,4,4-benzophenonetetracarboxylic dianhydride (BTDA) ), And 3,3,4,4-diphenyl ether tetracarboxylic dianhydride (ODPA) 31.02 g (0.1 mol), and after stirring for about 1 hour while reacting, 2,2-bis 29.3 g (0.08 mol) of (3-amino-4-hydroxyphenyl) hexafluoropropane (BAFA) is added and stirred at room temperature for about 3 hours. Next, 90 g of toluene was added, the temperature was raised to 150 ° C., and an imidization (cyclization) reaction was performed for 24 hours. As a result, a polyimide having an OH group was obtained, and then 5.88 g (0 0.06 mol) and the reaction is continued for about 3 hours at room temperature, and then the resin is put into a large amount of methanol to precipitate a polyimide polymer, thereby obtaining 111.3 g of polyimide polymer (PI-3). (Production rate: 92.3%, IV 0.67, Td: 335 ° C.).

Comparative Synthesis Example 1
41.05 g (0.1 mol) of 2,2′-bis- (4- [4-aminophenoxy] phenyl) propane (BAPP), 9.14 g (0.06 mol) of 3,5-diaminobenzoic acid (DABZ) ), And 350 g of NMP in 1 L of a glass reaction bottle, and after vigorously stirring at room temperature, 88.84 g of 2,2′-bis (3,4-dicarboxylphenyl) hexafluoropropane dianhydride (6FDA) ( 0.2 mol), and after stirring for about 1 hour while reacting, 8.43 g (0.039 mol) of 3,3′-dihydroxy-4,4′-diamino-biphenyl (HAP) was added, Stir at room temperature for about 3 hours. Next, 50 g of toluene is added, the temperature is raised to 150 ° C., the reaction is performed for 24 hours, and then the resin is put into a large amount of methanol to precipitate a polyimide polymer, whereby a polyimide polymer (PI-C) is obtained. 137.3 g is obtained (Production rate: 93.1%, IV 0.79, Td: 343 ° C.).
Table 1 below shows the composition and physical data of the reactants of the above synthesis examples and comparative synthesis examples.

Production Example 1 Production of Photosensitive Photoresist Protective Film (Coverlay) PI-1 20 g, IR 651 (photopolymerization initiator) 0.8 g, ethylene glycol diacrylate (M-1) 7.2 g, and triethylolpropane trimeta When 2.8 g of acrylate (M-2) is dissolved in 124 g of NMP and stirred at room temperature for about 3 hours, photosensitive PI glue (V-1) is obtained.
Using a doctor blade (gap = 100 μm), the above PI glue was applied to polyethylene terephthalate (PET), then dried at 90 ° C. for about 13 minutes, and the dried PI film was placed on a transfer machine. A copper foil is laminated at a temperature of 1 ° C. and a pressure of 1 kgf / cm 2, but the laminate is subjected to ultraviolet exposure using a photomask on which a predetermined pattern is formed (model number ORC-OB-1000, ORC MANUFACTRUING CO., Manufactured). ) (500 mJ / cm 2), followed by development with a 1 wt% Na ₂ CO ₃ aqueous solution for 2 minutes, followed by washing with fresh water, followed by 100 ° C./1 hour, 150 ° C./1 hour, 200 Dry at ℃ / 1 hour, 250 ℃ / 2 hours, and observe the pattern of the formed photoresist using a magnifier and a scanning electron microscope , Analysis / adhesion is 100/100 [mu] m.
Solubility test:
After casting the obtained polyimide and forming a film, a film having a size of 9 * 5.5 cm ² is dissolved in 1000 ml of a 1 wt% Na ₂ CO ₃ aqueous solution. If it completely dissolves within 2 minutes, the solubility is “good” "If the undissolved material remains even after 2 minutes or more, the solubility is" not good ".

Production Example 2 Production of Photosensitive Photoresist Protective Film PI-2 20 g, IR907 (trade name of Ciba-Geigy Chemical Company, 2-methyl-1- [4- (methylthio) phenyl])-2-morpholino-propane- 1-one) 0.75 g, ITX (2-isopropylthioxanthone) 0.15 g, ethylene glycol diacrylate (M-1) 6 g, triethylolpropane trimethacrylate (M-2) 3.5 g, pentaerythritol diacrylate ( M-3) Dissolve 2.5 g in NMP 130 g and stir at room temperature for about 3 hours to obtain photosensitive PI glue (V-2). The production of the protective film and the solubility test of Na2CO3 aqueous solution are Performed as in Example 1.

Production Example 3 Production of Photosensitive Photoresist Protective Film PI-3 20 g, IR907 0.53 g, ITX 0.2 g, ethylene glycol diacrylate (M-1) 3.5 g, pentaerythritol diacrylate (M-3) 4 g and 2.1 g of isocyanuric acid-tri (ethylene acrylate) (M-4) are dissolved in 119 g of NMP and stirred at room temperature for about 3 hours to obtain photosensitive PI glue (V-3). The production of the membrane and the solubility test of the Na2CO3 aqueous solution were carried out in the same manner as in Production Example 1.

Comparative Production Example 1 Production of Photosensitive Photoresist Protective Film PI-C 20 g, IR651 (2,2-dimethoxy-2-phenylacetophenone) 0.8 g, ethylene glycol diacrylate (M-1) 7.2 g, and trie Chi trimethylolpropane trimethyl acrylate (M-2) 2.8g were dissolved in NMP 124 g, after stirring for about 3 hours at room temperature, photosensitive PI glue (V-C) is obtained, the fabrication of the protective film and the Na ₂ The solubility test of the CO ₃ aqueous solution was performed in the same manner as in Production Example 1.
Table 2 below shows the test results of the preparation ratio and solubility of the photosensitive photoresist protective film.

Obviously from Table 2, the photosensitive polyimide polymer of the present invention has a photosensitive functional group and an acid group in the main chain, and thus exhibits high solubility in an alkaline aqueous solution. Since it is directly connected to the main chain of the polymer, Td is relatively high, and after exposure / development, the film thickness is hardly reduced by drying.

Claims (9)

Having an overlapping structure represented by the following formula (I):
And each said overlapping structure may be a block copolymer or a random polymer, The water-soluble photosensitive polyimide polymer characterized by the above-mentioned. The weight average molecular weight is 10,000 to 300,000, the intrinsic viscosity (IV) is 0.20 to 0.95, and the 5% thermal weight loss temperature (Td (95%)) is 260 ° C. or higher. The water-soluble photosensitive polyimide polymer according to claim 1. When water-soluble photosensitive polyimide polymer is applied as a film having a thickness of 10 to 25 μm, the time required for dissolving a film having a size of 9 × 5.5 cm ² in 1000 ml of 1 wt% sodium carbonate aqueous solution is 2 minutes or less. The water-soluble photosensitive polyimide polymer according to claim 1. Having an overlapping structure represented by the following formula (I):
And each said overlapping structure is a manufacturing method of the water-soluble photosensitive polyimide polymer characterized by being a block copolymer or a random polymer, This method includes the following process,
(A) By reacting a tetracarboxylic dianhydride with a diamine having a carboxyl group and / or a hydroxy functional group at normal pressure and room temperature to 90 ° C., the main chain has a carboxyl group and / or a hydroxy functional group. A polyamic acid precursor is synthesized, in which case the molar equivalent ratio of tetracarboxylic dianhydride to diamine (tetracarboxylic dianhydride: diamine) is 1: 0.8 to 1: 1.2,
(B) Next, the polyamic acid precursor having the carboxyl group and / or the hydroxy functional group in the main chain obtained in the above (a) is heated and cyclized at a temperature of 60 to 200 ° C., thereby forming the main chain. Synthesizing a polyimide having a carboxyl group and / or a hydroxy functional group;
(C) Furthermore, the hydroxy group of the polyimide having a carboxyl group and / or a hydroxy functional group in the main chain obtained in (b) above and the dianhydride of the following formula (II) are converted into the ring opening of the anhydride. Depending on the reaction
A method for producing a water-soluble photosensitive polyimide polymer, comprising synthesizing a polyimide polymer having an acrylic acid group having an overlapping structure represented by the above formula (I). The production method according to claim 4, wherein the diamine having a carboxyl group and / or a hydroxy functional group used in the step (a) is a diamine having a functional group of a hydroxy group and a carboxyl group. The production method according to claim 4, wherein a part of the diamine having a carboxyl group and / or a hydroxy functional group used in the step (a) is substituted with a diamine having a siloxane functional group. The production method according to claim 6, wherein the diamine having a siloxane functional group accounts for 5 to 60 mol% of the total diamine. The diamine having a siloxane functional group is 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane (DSI), 1,3-bis (4-aminobutyl) -1 , 1,3,3-tetramethyldisiloxane, 1,3-bis (3-aminopropyl) -1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-bis (3-aminophenyl)- 1,1,3,3-tetramethyldisiloxane, 1,3-bis (4-aminophenyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (3-aminophenoxylmethyl) ) -1,1,3,3-tetramethyldisiloxane, at least one selected from the group consisting of 1,3-bis (4-aminophenoxylmethyl) -1,1,3,3-tetramethyldisiloxane To be The method according to claim 7, symptoms. (A) a water-soluble photosensitive polyimide polymer having an overlapping structure of formula (I) according to claim 1, (B) a (meth) acrylic acid monomer diluent, and (C) a photoinitiator, and a component The weight ratio of (A): component (B) is 100: 10-200, and the content of component (C) photoinitiator is 0.1-15. A soluble photosensitive polyimide resin composition characterized by being 0% by weight.