CN101776847A - Water soluble light-sensitive polyimide polymer, method for preparing same and photoresistive composition containing same - Google Patents
Water soluble light-sensitive polyimide polymer, method for preparing same and photoresistive composition containing same Download PDFInfo
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- CN101776847A CN101776847A CN200910001495A CN200910001495A CN101776847A CN 101776847 A CN101776847 A CN 101776847A CN 200910001495 A CN200910001495 A CN 200910001495A CN 200910001495 A CN200910001495 A CN 200910001495A CN 101776847 A CN101776847 A CN 101776847A
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Abstract
The invention relates to a water soluble light-sensitive polyimide polymer, a method for preparing the same and a photoresistive composition containing the same, wherein the water soluble light-sensitive polyimide polymer is characterized by comprising recurring units of a formula below, wherein R1 is a tetravalent organic group having more than four carbon atoms; R2 is a trivalent or tetravalent organic group, and may also have a carboxyl group if required; R3 represents bivalent to tetravalent organic groups; A represents an OH or COOH group; R4 and R5 may be the same or different and represent alkylidene groups having 1 to 6 carbon atoms and arylidene groups, aralkyl groups and aryloxy alkylidene groups, which have 6 to 20 carbon atoms respectively; R7 and R8 may be the same or different and are independently selected from hydrogen, halogens, carboxyl groups, straight chain or ring chain alkyl groups having 1 to 20 carbon atoms, and aryl groups, alkaryl groups and aralkyl groups having 6 to 20 carbon atoms; R9 represents a hydrogen atom or alkyl groups having 1 to 6 carbon atoms; x represents an integer of 1 or 2; y represents 0, 1 or 2; a, b and n represent integers more than or equal to 1; and m and k represent integers more than 0.
Description
Technical field
The relevant a kind of water soluble light-sensitive polyimide polymer of the present invention with and method for making.In detail, be relevant a kind of to organic solvent and alkaline aqueous solution have good solubility, after film forming, have excellent heat resistance, the water soluble light-sensitive polyimide polymer of flexible and electrical insulation characteristics, and can be widely used in electronic industry.
Background technology
In manufacture of semiconductor, the favourable light photolithography techniques of using is drawn in the enterprising line of substrate road, be necessary to use the sensing optical activity resin in this photolithography techniques, by the sensing optical activity of sensing optical activity resin to radiant rays, and can be after seeing through the light shield exposure with required pattern, utilize eccysis exposed part or unexposed parts such as aqueous slkali, can obtain to have the printed circuit board (PCB) of required pattern.
Used sensing optical activity resin in the light lithography etching technique, have an exploitation more.For example disclose a kind of polyimide precursor in US 5587275 patent cases, it has the structural units shown in the following formula (1):
Wherein X is the quadrivalent organic radical with aromatic ring; Y is the divalent organic base that has the divalent organic base of aromatic ring or have siloxane bond; Z is hydrogen atom or has acryloxy or the methacryloxy shown in the following formula (2):
Wherein R is hydrogen atom or methyl.
These US 5587275 patents are to make diamines and the reaction of (methyl) acrylic acid glycidol ether earlier, after acquisition has the diamine monomer of acryloxy, again with the tetracarboxylic dianhydride monomer reaction, obtain the polyimide precursor of above-mentioned formula (1).
The polyimide precursor that has the recurring unit that represents with following formula (3) and formula (4) in addition in 6025113 announcements of US:
R wherein
1For containing 4 or the quadrivalent organic radical of more carbon atoms; R
2Be trivalent or the quadrivalent organic radical that contains at least one aromatic ring; R
3Be the unit price organic group; A is acid unit price base; And n is 1 or 2;
R wherein
1For containing 4 or the quadrivalent organic radical of more carbon atoms; R
3Be the unit price organic group; R
4For containing the divalent organic base of at least one aromatic ring or silicon atom.
These US 6025113 patents are to utilize to form ester bond between acryloyl group and polyamic acid to improve the photoresistance light sensitivity, behind exposure imaging, utilize the high temperature cyclisation to form again and have high-fire resistance and flexible polyimide at last.
The inventor etc. have water miscible photosensitive polyimide resin for developing, and the functional group of these preparation polyimide resins is inquired into, thereby finish the present invention.
Summary of the invention
In view of the above, the invention provides a kind of water soluble light-sensitive polyimide polymer, it is characterized by the have following formula recurring unit of (I):
In the formula, R
1For containing the quadrivalent organic radical of 4 above carbon atoms; R
2Be 3 valencys or 4 valency organic groups, can have carboxyl according to circumstances again on it; R
3Expression divalent to 4 valency organic group; A represents OH or COOH base; R
4And R
5Can be identical also can be different, be expressed as the alkylidene that contains 1 to 6 carbon atom, the arlydene that contains 6 to 20 carbon atoms, inferior aralkyl, inferior aryloxy group alkylidene respectively; R
7And R
8Can be identical or different and independent for being selected from hydrogen, halogen, carboxyl, the straight chain that contains 1-20 carbon or cyclic alkyl, the aryl that contains 6-20 carbon atom, alkaryl and aralkyl; R
9Expression hydrogen atom or contain the alkyl of 1 to 6 carbon atom; X represents 1 or 2 integer; Y represents 0,1 or 2 integer; A, b and n represent the integer more than or equal to 1; M and k represent the integer greater than 0; And above-mentioned each recurring unit can be block polymerization and also can be polymerization at random.
The weight average molecular weight Mw that converts the polystyrene meter to by gel permeation chromatography (GPC) of water soluble light-sensitive polyimide polymer of the present invention is about 10,000～300,000, preferablely be about 20,000～150,000, its intrinsic viscosity (IV) is preferably 0.20～0.95, be preferably 0.60～0.85, and its 5% thermogravimetric loss temperature (Td (95%)) is lower than 350 ℃, better is lower than 340 ℃.
Among the present invention, above-mentioned intrinsic viscosity is the polymer solution that polymer concentration is formulated as 0.5g/dL,, measure as solvent with N-methylpyrrole pyridine ketone (NMP), calculate the value of its intrinsic viscosity again with following formula with capillary viscometer (Ubbelohode viscometer):
η
inh＝ln(t/t0)/0.5(g/dl)
Wherein the t0=solvent is by the blank group time (second) of two scales about the viscosimeter
The t=polymer solution is by the time (second) of two scales about the viscosimeter.
Among the present invention, the temperature when above-mentioned 5% heat decomposition temperature (Td (95%)) is to use resin 5% thermal decomposition that thermogravimetric analyzer (TGA) measures.
Solubleness excellence in the water soluble light-sensitive polyimide polymer alkaline aqueous solution of the present invention is when coating film forming (thickness 10～25 μ m), with diaphragm (size: 9*5.5cm
2) dissolution time that is dissolved in 1000 milliliters the 1wt% aqueous sodium carbonate is less than 2 minutes, shows to have good aqueous alkali solubleness.
The relevant again a kind of preparation of the present invention has the method for water soluble light-sensitive polyimide polymer of the recurring unit of following formula (I):
In the formula, R
1For containing the quadrivalent organic radical of 4 above carbon atoms; R
2Be 3 valencys or 4 valency organic groups, can have carboxyl according to circumstances again on it; R
3Expression divalent to 4 valency organic group; A represents OH or COOH base; R
4And R
5Can be identical also can be different, be expressed as the alkylidene that contains 1 to 6 carbon atom, the arlydene that contains 6 to 20 carbon atoms, inferior aralkyl, inferior aryloxy group alkylidene respectively; R
7And R
8Can be identical or different and independent for being selected from hydrogen, halogen, carboxyl, the straight chain that contains 1-20 carbon or cyclic alkyl, the aryl that contains 6-20 carbon atom, alkaryl and aralkyl; R
9Expression hydrogen atom or contain the alkyl of 1 to 6 carbon atom; X represents 1 or 2 integer; Y represents 0,1 or 2 integer; A, b and n represent the integer more than or equal to 1; M and k represent the integer greater than 0; Wherein respectively repeat single for can be block polymerization or atactic polymerization;
This method comprises the following steps:
(a) tetracarboxylic dianhydride and the diamines with carboxyl and/or hydroxyl-functional base are reacted, obtain to have on the main chain polyamic acid precursor of carboxyl and/or hydroxyl-functional base; Wherein the tetracarboxylic dianhydride is the tetracarboxylic dianhydride to the molar equivalent ratio of diamines: diamines=1: 0.8～1: 1.2.
(b) make the polyamic acid precursor that has carboxyl and/or hydroxyl-functional base on the main chain of above-mentioned (a) gained heat cyclisation, obtain to have on the main chain polyimide of carboxyl and/or hydroxyl-functional base; And
(c) make the dicarboxylic anhydride of hydroxyl in the polyimide that has carboxyl and/or hydroxyl-functional base on the main chain of above-mentioned (b) gained and following formula (II) carry out the ring-opening reaction of acid anhydrides:
In the formula,
R
7And R
8Can be identical or different and independent for being selected from hydrogen, halogen, carboxyl, the straight chain that contains 1-20 carbon or cyclic alkyl, the aryl that contains 6-20 carbon atom, alkaryl and aralkyl; R
9Expression hydrogen atom or contain the alkyl of 1 to 6 carbon atom;
Acquisition has the polyimide polymer that above-mentioned general formula (I) represents to have on the main chain of recurring unit acrylic.
In the method for the present invention, the used diamines with carboxyl and/or hydroxyl-functional base also can use the diamines that only has the carboxyl-functional base, the diamines that only has the diamines of hydroxyl-functional base and have the functional group of hydroxyl and carboxyl simultaneously in the above-mentioned steps (a).In only using diamines during, can obtain the polymeric unit that A in the above-mentioned general formula (I) only represents OH as initial diamines with hydroxyl; And by the value of content may command m of control dicarboxylic anhydride (II), when for example dicarboxylic anhydride (II) equivalent equated with hydroxyl equivalent, m became 0, and during greater than dicarboxylic anhydride (II) equivalent, m becomes greater than 0 in hydroxyl equivalent.When using the functional group's who has hydroxyl and carboxyl simultaneously diamines, can obtain the polymeric unit that the middle A of above-mentioned general formula (I) represents OH and COOH; And by the value of content may command m of control dicarboxylic anhydride (II), when for example dicarboxylic anhydride (II) equivalent equated with hydroxyl equivalent, m became 0, and when containing dicarboxylic anhydride (II) equivalent, m becomes greater than 0 in hydroxyl equivalent.
In the method for the present invention, the diamines with carboxyl and/or hydroxyl-functional base used in the above-mentioned steps (a) also can partly be replaced through the diamines with siloxane functional group.
The diamines that has the siloxane functional group among the present invention is following diamines:
In the method for the present invention, used diamines in the above-mentioned steps (a), except above-mentioned diamines and have siloxane functional group's the diamines with carboxyl and/or hydroxyl-functional base, in the scope that does not undermine the final polyimide resin desired properties of the present invention, can and use again and make diamines commonly used in the polyimide resin.
In the method for the present invention, the condensation reaction of above-mentioned steps (a) is ℃ to carry out in room temperature to 90 under normal pressure, is preferably 30～75 ℃; And the cyclization of step (b) is at 60～200 ℃, carries out under 90～150 ℃ the temperature more fortunately.
In the method for the present invention, in the above-mentioned steps (a), under the diamines with carboxyl and/or hydroxyl-functional base can the situation that partly diamines through having the siloxane functional group is replaced, there is no particular restriction for its ratio between the two, as long as the tetracarboxylic dianhydride to the molar equivalent ratio of diamines total amount in above-mentioned scope, but better this diamines with siloxane functional group accounts for 5～60 moles of % of all diamines, and more preferably 10～40 moles of % are preferably 15～20 weight %.
Polyimide polymer of the present invention can use as photoresist, and in for example coating as photoresist on the substrate on the copper base and after the exposure of developing, and, also can not cause the thickness reduction because of baking through postexposure bake.And polyimide polymer of the present invention directly is connected on the high polymer main chain because of the sensing optical activity functional group, and has higher Td (95%).
The relevant again a kind of solubility light-sensitive polyimide resin combination of the present invention, it comprises that (A) has the water soluble light-sensitive polyimide polymer of the recurring unit of above-mentioned formula (I); (B) (methyl) acrylic monomers thinning agent; And (C) light initiator.Composition (A) wherein: the part by weight of composition (3) is 100: 10～200, be preferably 100: 40～and 100.The light initiator of composition (C), when being 100 weight % with composition (A), its contained ratio is 0.1～15.0 weight %, is preferably 1.0～5.0 weight %.
Embodiment
Can give an example as (but being not limited to) 2,2 '-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride (6FDA) in order to used tetracarboxylic dianhydride's example in the method step (a) of preparation polyimide among the present invention, pyromellitic dianhydride (PMDA), 4,4 '-oxygen base, two anhydride phthalic acids (ODPA), 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride (BPDA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), the ethylidene tetracarboxylic dianhydride, the butane tetracarboxylic acid dianhydride, the cyclopentane tetracarboxylic dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 2, two (3,4-dicarboxyl phenyl) the propane dianhydrides of 2-, 2,2-two (2,3-dicarboxyl phenyl) propane dianhydride, two (3,4-dicarboxyl phenyl) ether dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, 1,1-two (2,3-dicarboxyl phenyl) ethane dianhydride, two (2,3-dicarboxyl phenyl) methane dianhydride, two (3,4-dicarboxyl phenyl) methane dianhydride, 4,4 '-(right-benzene dioxy base) two phthalandione dianhydrides, 4,4 '-(-benzene dioxy base) two phthalandione dianhydrides, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 1,2,3,4-benzene tertacarbonic acid dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride and 1,2,7, the luxuriant and rich with fragrance tetracarboxylic dianhydride of 8-etc.Described dicarboxylic anhydride can be used alone or use with multiple potpourri.Wherein be preferably:
Among the present invention in the method step (a) of preparation polyimide employed diamines example with carboxyl and/or hydroxyl-functional base can give an example as (but being not limited to) for example 3,5-diamines yl benzoic acid (DABZ), 3,3 '-dihydroxy-4,4 '-benzidine etc.
Among the present invention in the method step (a) of preparation polyimide employed diamines with siloxane functional group for example can be exemplified as 1, two (the 3-aminocarbonyl propyls)-1,1 of 3-, 3,3-tetramethyl disiloxane (DSI), 1, two (the 4-amido butyl)-1 of 3-, 1,3, the 3-tetramethyl disiloxane, 1, two (the 3-aminocarbonyl propyls)-1 of 3-, 3-dimethyl-1,3-diphenyl disiloxane, 1, two (the 3-aminocarbonyl phenyls)-1 of 3-, 1,3, the 3-tetramethyl disiloxane, 1, two (the 4-aminocarbonyl phenyls)-1 of 3-, 1,3, the 3-tetramethyl disiloxane, 1, two (the 3-amido phenoxymethyls)-1 of 3-, 1,3, the 3-tetramethyl disiloxane, 1, two (the 4-amido phenoxymethyls)-1 of 3-, 1,3,3-tetramethyl disiloxane etc.
In the method step of preparation polyimide of the present invention (a), except above-mentioned diamines and have diamines siloxane functional group's the diamines with carboxyl and/or hydroxyl-functional base, for example right-phenyl diamines (PDA) can be arranged for example, 4,4 '-oxygen base diphenylamine (ODA), 1, two (the 4-amido phenoxy group) benzene (TPE-R) of 3-, 2, two [4-(the 4-amido phenoxy group) phenyl] propane (BAPP) of 2-, two [4-(4-amido phenoxy group) phenyl] sulfone (BAPS), 1, two (the 3-amido phenoxy group) benzene (APB) of 3-, 4,4 '-two (4-amido phenoxy groups)-3,3 '-dihydroxybiphenyl (BAPB), two [4-(3-amido phenoxy group) phenyl] methane, 1, two [4-(the 3-amido phenoxy group) phenyl] ethane of 1-, 1, two [4-(the 3-amido phenoxy group) phenyl] ethane of 2-, 2, two [4-(the 3-amido phenoxy group) phenyl] propane of 2-, 2,2 '-two [4-(3-amido phenoxy group) phenyl] butane, 2, two [4-(the 3-amido phenoxy group) phenyl]-1 of 2-, 1,1,3,3, the 3-HFC-236fa, 4,4 '-two (3-amido phenoxy group) biphenyl, two [4-(3-amido phenoxy group) phenyl] ketone, two [4-(3-amido phenoxy group) phenyl] thioether, two [4-(3-amido phenoxy group) phenyl] sulfoxide, two [4-(3-amido phenoxy group) phenyl] sulfone, two [4-(3-amido phenoxy group) phenyl] ether etc.Above-mentioned diamine can be used alone or use with multiple mixing.
In the method step of preparation polyimide of the present invention (a), the reaction of this dicarboxylic anhydride and diamines can be carried out in aprotic polar solvent, and there is no particular restriction for the kind of aprotic polar solvent, only otherwise get final product with reactant and product reaction.Instantiation can be given an example as N,N-dimethylacetamide (DMAc), N-Methyl pyrrolidone (NMP), N, dinethylformamide (DMF), tetrahydrofuran (THF), dioxan, chloroform (CHCl3), methylene chloride etc.Wherein better use N-Methyl pyrrolidone (NMP) and N,N-dimethylacetamide (DMAc).
In the method step of preparation polyimide of the present invention (a), the reaction of this dicarboxylic anhydride and diamines generally in room temperature to 90 ℃, is carried out in better 30 to the 75 ℃ temperature range.
In the method for preparing polyimide of the present invention, in step (c), methylene phthalic anhydride that dicarboxylic anhydride (II) can be exemplified as maleic anhydride, the maleic anhydride that is substituted, tetrabydrophthalic anhydride, the tetrabydrophthalic anhydride that is substituted, methylene phthalic anhydride, be substituted etc.
In the solubility light-sensitive polyimide resin combination of the present invention, (methyl) acrylic monomers thinning agent of composition (B) is except that the function as thinning agent, because its molecule contains the ethene functional group, so also help the sclerosis behind the composition irradiation, the example can be exemplified as for example glycol diacrylate, propylene glycol diacrylate, butanediol diacrylate, diethylene glycol diacrylate, propylene glycol diacrylate, trimethylolpropane triacrylate, the triethylol propane triacrylate, pentaerythritol diacrylate, the dipentaerythritol triacrylate, ethylene glycol dimethacrylate, the propylene glycol dimethylacrylate, butanediol dimethylacrylate, the diethylene glycol dimethylacrylate, the dipropylene glycol dimethylacrylate, trimethylol-propane trimethacrylate, the triethylol propane trimethyl acrylic ester, season penta dimethylacrylate, dipentaerythritol trimethyl acrylic ester etc.
Polyimide resin of the present invention is when being modulated to photoresist, and adjustable be furnished with the light initiator.Light initiator used in the allotment photoresistance composition of the present invention is for being subjected under the radiant light irradiations such as visible light, ultraviolet light, extreme ultraviolet light, electron beam and X ray, cracking can take place and produce as free radical, kation or negative ion isoreactivity site (Active site) in its molecular structure, and makes polyimide and acrylate monomer carry out polyreaction persons.
Light initiator example can be given an example as imidazoles as 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-wantonly (4-ethoxy carbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-wantonly (4-ethoxy carbonyl phenyl)-1,2 '-diimidazole, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole and 2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-diimidazole.
Light initiator example can be given an example as triphenylphosphine oxidation thing (TPO, can available from BASF AG), as two (2,4, the 6-trimethylbenzoyl) phenylphosphine oxide (Irgacure 819 (IR819) is available from Ciba Geigy company); The alkyl phenyl ketone, for example the 1-hydroxycyclohexylphenylketone [as with Irgacure 184 (IR184) available from Ciba Geigy company], 2-methyl-(4-methylthiophene base)-2-morpholine-1-third-1-ketone, as with Irgacure 907 (IR907) available from CibaGeigy company etc.
Light initiator example can give an example again as benzoin (Benzoin) class light initiator for example benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether, benzoin isobutyl ether, methyl-2-benzoyl benzoic ether etc. with and like derivatives.
Light initiator example can be given an example as the acetophenones structure example again as 2,2-dimethoxy-2-phenyl acetophenone [as with Irgacure 651 (IR651) available from Ciba Geigy company], 2-hydroxy-2-methyl-1-phenyl third-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 2, the 2-dimethoxy-acetophenone, 2, the 2-diethoxy acetophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) fourth-1-ketone, 2,2 '-dimethoxy-1,2-diphenyl second-1-ketone, 4-triazobenzene ethyl ketone, 4-azido benzylidene acetophenone etc. and like derivatives.
Light initiator example can be given an example again as benzophenone such as benzophenone, 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylin) benzophenone, 3,3 '-dimethyl-4-methoxy benzophenone etc. and like derivatives thereof.
Light initiator example can be given an example again as having the light initiator of α-diketone structure, for example diacetyl formic ether, dibenzoyl carbamate, toluyl carbamate etc. and like derivatives;
Have the light initiator of multinuclear quinone structure such as anthraquinone, 2-EAQ, 2-tributyl anthraquinone, 1,4-naphthoquinones etc. and like derivatives; The light initiator of xanthene ketone (xanthone) structure such as xanthone, thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone etc. and like derivatives;
Have the light initiator of diazonium structure such as 4-diazonium diphenylamine, 4-diazonium-4 '-methoxyl diphenylamine, 4-azido-3-methoxyl diphenylamine etc. and like derivatives; Light initiator such as 2-(2 '-furyl ethylidene)-4 with triazine structure, two (the trichloromethyl)-s-triazines of 6-, 2-(3 ', 4 '-dimethoxy-styryl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4 '-methoxyl naphthyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(2 '-bromo-4 '-aminomethyl phenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(2 '-thienyl ethylidene)-4, two (trichloromethyl)-s-triazines of 6-etc. and like derivatives.
Described smooth initiator can also use separately can mix two or more uses.With respect to composition (A) is 100 weight % timing, and the use amount of this light initiator (C) is 0.1～15.0 weight %, is preferably 1.0～5.0 weight %.
The present invention will further describe in detail with following synthesis example and embodiment, but described synthesis example and embodiment purpose are only in order to explanation the present invention but not in order to limit the scope of the invention.
Synthesis example 1
With 2 of 41.05 grams (0.1 mole), 3 of 2 '-two-[4-(4-amido phenoxy group) phenyl] propane (BAPP) and 9.14 grams (0.06 mole), 5-diamines yl benzoic acid (DABZ) and 350 gram N-methylpyrrole pyridine ketone (NMP) are inserted in 1 liter of glass reaction bottle, at room temperature high degree of agitation.2,2 '-two (3,4-dicarboxyl phenyl) the HFC-236fa dicarboxylic anhydride (6FDA) that adds 88.48 grams (0.2 mole) stirs after 1 hour in reaction bulb, add 8.43 gram (0.039 moles) 3 again, 3 '-dihydroxy-4,4 '-benzidine (HAP) was in stirring at room 3 hours.Then add 50 gram toluene, imidizate (cyclisation) reaction was carried out in increase in temperature to 150 a ℃ reaction in 24 hours, obtained to have the polyimide of OH base, then added the maleimide (MA) of 3.92 grams (0.04 mole), continued reaction 3 hours under room temperature.Then this resin is poured in a large amount of methyl alcohol and separated out, can obtain 136.2 gram polyimide polymers (PI-1) (productive rate: 90.01%, IV is 0.81, Td (95%): 340 ℃).
Synthesis example 2
15.215 3 of gram (0.1 mole), the NMP of 5-diamines yl benzoic acid (DABZ) and 200 grams inserts in the glass reaction axe of 1L, at room temperature vigorous stirring.Add 2 of 44.42 grams (0.1 mole), 2 '-two (3,4-dicarboxyl phenyl)-HFC-236fa dicarboxylic anhydride (6FDA) and 32.22 the gram (0.1 mole) 3,3,4,4-benzophenone tetracarboxylic dianhydride (BTDA), in reaction, stir after 1 hour, add 3 of 21.19 grams (0.098 mole) again, 3 '-dihydroxy-4,4 '-benzidine stirred in room temperature 3 hours.The toluene that add 30 grams then improve temperature to 150 a ℃ reaction and carried out imidizate (cyclisation) reaction in 24 hours, can obtain a polyimide that has the OH base, and then the maleic anhydrides that add 5.88 grams (0.06 mole) continue to react 3 hours in room temperature.Then this resin is poured in a large amount of methyl alcohol and separated out, can obtain the polyimide polymer (PI-2) (productive rate: 94.8%, IV is 0.76, Td:336 ℃) of 112.7g.
Synthesis example 3
15.215 3 of gram (0.1 mole), 1 of 5-diamines yl benzoic acid and 3.847 grams (0.02 mole), two (the 3-aminocarbonyl propyls)-1,1,3 of 3-, the NMP of 3-tetramethyl disiloxane (DSI) and 460 grams inserts in the glass reaction axe of 1L, at room temperature vigorous stirring.Add 3 of 32.22 grams (0.1 mole), 3,4,3 of 4-benzophenone tetracarboxylic dianhydride (BTDA) and 31.02 grams (0.1 mole), 3,4,4-diphenyl ether tetracarboxylic dianhydride (ODPA) stirs after 1 hour in reaction, add 2 of 29.3 grams (0.08 mole) again, two (3-amido-4-hydroxy phenyl) HFC-236fa (BAFA) of 2-stirred 3 hours in room temperature.The toluene that add 90 grams then improve temperature to 150 a ℃ reaction and carried out imidizate (cyclisation) reaction in 24 hours, can obtain having the polyimide of OH base, and then the maleic anhydrides that add 5.88 grams (0.06 mole) continue to react 3 hours in room temperature.Then this resin is poured in a large amount of methyl alcohol and separated out, can obtain the polyimide polymer (PI-3) (productive rate: 92.3%, IV is 0.67, Td:335 ℃) of 111.3g.
Compare synthesis example 1
41.05 3 of 2,2 ' of gram (0.1 mole)-two-(4-[4-amido phenoxy group] phenyl) propane (BAPP) and 9.14 grams (0.06 mole), 5-diamines yl benzoic acid (DABZ) and 350 NMP that restrain insert in the glass reaction axe of 1L, at room temperature vigorous stirring.Add 2 of 88.84 grams (0.2 mole), 2 '-two (3,4-dicarboxyl phenyl) HFC-236fa dicarboxylic anhydride (6FDA) stirs after 1 hour in reaction, adds 3 of 8.43 grams (0.039 mole) again, 3 '-dihydroxy-4,4 '-two amidos-biphenyl (HAP) stirred 3 hours in room temperature.The toluene that add 50 grams then improve temperature to 150 ℃ reaction 24 hours, this resin is poured in a large amount of methyl alcohol separated out then, can obtain the polyimide polymers (PI-C) (productive rate: 93.1%, IV is 0.79, Td:343 ℃) of 137.3 grams.
The reactant of above-mentioned synthesis example and comparative example, its amount and physical data thereof are summarized in following table 1.
Table 1
| Synthesis example 1 (PI-1) | Synthesis example 2 (PI-2) | Synthesis example 3 (PI-3) | Compare synthesis example 1 (PI-C) | |
| BAPP (mole) | ??0.1 | ??0.1 | ||
| DABZ (mole) | ??0.06 | ??0.1 | ??0.1 | ??0.06 |
| HAP (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 | |||
| MA (mole) | ??0.04 | ??0.098 | ??0.06 | |
| ??DSI | ??0.02 | |||
| IV (intrinsic viscosity) | ??0.81 | ??0.76 | ??0.67 | ??0.79 |
| ??Td(95％)(℃) | ??340 | ??336 | ??335 | ??343 |
The making of Production Example 1 sensitization photoresistance diaphragm (Coverlay)
The triethylol propane trimethyl acrylic ester (M-2) of the glycol diacrylate (M-1) of the IR651 (photopolymerization initiator) of the PI-1 of 20 grams, 0.8 gram, 7.2 grams and 2.8 grams, be dissolved in the NMP of 124g, and after 3 hours, can obtain sensitization PI glue (V-1) in stirring at room.
Use scraper plate coating (gap=100 μ m) that PI glue is coated on the polyphenyl dioctyl phthalate second diester (PET), and with baking in 90 ℃/13 minutes.With the PI film after its baking on transfer interpreter with 120 ℃, pressure 1kgf/cm and Copper Foil pressing.This laminate is had the light shield that sees through of required pattern, and (500mJ/cm exposes with ultraviolet exposure apparatus according (model ORC-OB-1000, ORC MANUFACTRUING CO. makes)
2), and use 1wt%Na
2CO
3Aqueous solution was developed 2 minutes, was soaked in the pure water to clean again.Then, 150 ℃/1 hour, 200 ℃/1 hour, toasted in 250 ℃/2 hours at 100 ℃/1 hour.Get the photoresistance pattern by magnifier and scanning electron microscope observation post, can be resolved/adherence is the wiring diagram of 100/100 μ m.
Solubility test:
With gained polyimide casting film, get size 9*5.5cm
2Be dissolved in 1000 milliliters 1wt%Na
2CO
3In the aqueous solution, dissolving person fully in 2 minutes is expressed as solubleness " good ", still leave not dissolved matter if surpass 2 minutes, then be expressed as solubleness " not good ".
The making of Production Example 2 sensitization photoresistance diaphragms
The IR907 of the PI-2 of 20 grams, 0.75 gram (the special chemical company trade name of using of Ciba-Geigy, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl])-2-morpholinyl-third-1-ketone), 0.15 the gram ITX (2-isopropyl thioxanthone), 6 the gram glycol diacrylates (M-1) and the triethylol propane trimethyl acrylic ester (M-2) of 3.5g, 2.5g pentaerythritol diacrylate (M-3) be dissolved in the NMP of 130g, and after 3 hours, can obtain sensing optical activity PI glue (V-2) in stirring at room.The making of diaphragm and Na
2CO
3The aqueous solubilities test is identical with making example 1.
The making of Production Example 3 sensitization photoresistance diaphragms
The isocyanuric acids three (ethane acrylate) that the pentaerythritol diacrylates (M-3) of the glycol diacrylates (M-1) of the ITX of the IR907 of the PI-3 of 20 grams, 0.53 gram, 0.2 gram, 3.5 grams and 3.4 grams and 2.1 restrain (M-4) are dissolved in 119 NMP that restrain, and after 3 hours, can obtain sensing optical activity PI glue (V-3) in stirring at room.
The making of diaphragm and Na
2CO
3The aqueous solubilities test is identical with Production Example 1.
The relatively making of Production Example 1 sensitization photoresistance diaphragm
The IR651 (2 of the PI-C of 20 grams, 0.8 gram, 2-dimethoxy-2-phenyl acetophenone), the triethylol propane trimethyl acrylic ester (M-2) of the glycol diacrylate (M-1) of 7.2 grams and 2.8 grams, be dissolved in the NMP of 124 grams, and after 3 hours, can obtain sensitization PI glue (V-C) in stirring at room.The making of diaphragm and Na
2CO
3The aqueous solubilities test is identical with Production Example 1.
The allotment ratio and the solubility test of sensitization photoresistance diaphragm the results are shown in following table 2.
Table 2
| Composition (gram) | Production Example 1 (V-1) | Production Example 2 (V-2) | Production Example 3 (V-3) | Compare Production Example 1 (V-C) |
| Resin | ??PI-1(100) | ??PI-2(100) | ??PI-3(100) | ??PI-C(100) |
| ??IR651 | ??4.0 | ??4.0 | ||
| ??IR907 | ??3.75 | ??2.65 | ||
| ??ITX | ??0.75 | ??1.0 | ||
| ??M-1 | ??36.0 | ??30.0 | ??17.5 | ??36.0 |
| ??M-2 | ??14.0 | ??17.5 | ??14.0 |
| Composition (gram) | Production Example 1 (V-1) | Production Example 2 (V-2) | Production Example 3 (V-3) | Compare Production Example 1 (V-C) |
| ??M-3 | ??12.5 | ??17.0 | ||
| ??M-4 | ??10.5 | |||
| Resolution | ??100/100μm | ??80/100μm | ??100/100μm | ??200/250μm |
| Thickness economy (%) | About 11% | About 7% | About 8% | About 10% |
| ??Na 2CO 3Solubleness in the aqueous solution | Good | Good | Good | Not good |
As seen from the above table, photosensitive polyimide polymkeric substance of the present invention, owing on main chain, have the photonasty functional group, and have acidic group so have excellent solubility for aqueous alkali.In addition, the functional group directly is connected on the main polymer chain because of this sensing optical activity, so have higher Td, behind exposure imaging, also can seriously not reduce because of baking causes thickness.
Claims (9)
1. water soluble light-sensitive polyimide polymer is characterized by the have following formula recurring unit of (I):
In the formula, R
1For containing the quadrivalent organic radical of 4 above carbon atoms; R
2Be 3 valencys or 4 valency organic groups, can have carboxyl according to circumstances again on it; R
3Expression divalent to 4 valency organic group; A represents OH or COOH base; R
4And R
5Can be identical also can be different, be expressed as the alkylidene that contains 1 to 6 carbon atom, the arlydene that contains 6 to 20 carbon atoms, inferior aralkyl, inferior aryloxy group alkylidene respectively; R
7And R
8Can be identical or different and independent for being selected from hydrogen, halogen, carboxyl, the straight chain that contains 1-20 carbon or cyclic alkyl, the aryl that contains 6-20 carbon atom, alkaryl and aralkyl; R
9Expression hydrogen atom or contain the alkyl of 1 to 6 carbon atom; X represents 1 or 2 integer; Y represents 0,1 or 2 integer; A, b and n represent the integer more than or equal to 1; M and k represent the integer greater than 0; And above-mentioned each recurring unit can be block polymerization and also can be polymerization at random.
2. water soluble light-sensitive polyimide polymer as claimed in claim 1, wherein its weight average molecular weight is 10,000～300,000, its intrinsic viscosity (IV) be 0.20～0.95 and its 5% thermogravimetric loss temperature (Td (95%)) be higher than 300 ℃.
3. water soluble light-sensitive polyimide polymer as claimed in claim 1 is wherein when water soluble light-sensitive polyimide polymer coating film forming is thick when being the film of 10～25 μ m, with diaphragm size 9*5.5cm
2The dissolution time that is dissolved in 1000 milliliters the 1wt% aqueous sodium carbonate is less than 2 minutes.
4. one kind prepares the have following formula method of water soluble light-sensitive polyimide polymer of recurring unit of (I),
In the formula, R
1For containing the quadrivalent organic radical of 4 above carbon atoms; R
2Be 3 valencys or 4 valency organic groups, can have carboxyl according to circumstances again on it; R
3Expression divalent to 4 valency organic group; A represents OH or COOH base; R
4And R
5Can be identical also can be different, be expressed as the alkylidene that contains 1 to 6 carbon atom, the arlydene that contains 6 to 20 carbon atoms, inferior aralkyl, inferior aryloxy group alkylidene respectively; R
7And R
8Can be identical or different and independent for being selected from hydrogen, halogen, carboxyl, the straight chain that contains 1-20 carbon or cyclic alkyl, the aryl that contains 6-20 carbon atom, alkaryl and aralkyl; R
9Expression hydrogen atom or contain the alkyl of 1 to 6 carbon atom; X represents 1 or 2 integer; Y represents 0,1 or 2 integer; A, b and n represent the integer more than or equal to 1; M and k represent the integer greater than 0; Wherein respectively repeat single for can be block polymerization or atactic polymerization; This method comprises the following steps:
(a) tetracarboxylic dianhydride and the diamines with carboxyl and/or hydroxyl-functional base ℃ are reacted under normal pressure in room temperature to 90, obtain to have on the main chain polyamic acid precursor of carboxyl and/or hydroxyl-functional base; Wherein the tetracarboxylic dianhydride is the tetracarboxylic dianhydride to the molar equivalent ratio of diamines: diamines=1: 0.8～1: 1.2;
(b) make the polyamic acid precursor that has carboxyl and/or hydroxyl-functional base on the main chain of above-mentioned (a) gained heat cyclisation, obtain to have on the main chain polyimide of carboxyl and/or hydroxyl-functional base 60～200 ℃ temperature; And
(c) make the dicarboxylic anhydride of hydroxyl in the polyimide that has carboxyl and/or hydroxyl-functional base on the main chain of above-mentioned (b) gained and following formula (II) carry out the ring-opening reaction of acid anhydrides:
(Ⅱ)
In the formula,
R
7And R
8Can be identical or different and independent for being selected from hydrogen, halogen, carboxyl, the straight chain that contains 1-20 carbon or cyclic alkyl, the aryl that contains 6-20 carbon atom, alkaryl and aralkyl; R
9Expression hydrogen atom or contain the alkyl of 1 to 6 carbon atom;
Acquisition has the polyimide polymer with acrylic of above-mentioned general formula (I) expression recurring unit.
5. method as claimed in claim 4, wherein the used diamines with carboxyl and/or hydroxyl-functional base is the diamines with functional group of hydroxyl and carboxyl in the above-mentioned steps (a).
6. method as claimed in claim 4, wherein the used diamines with carboxyl and/or hydroxyl-functional base is partly to replace through the diamines with siloxane functional group in the above-mentioned steps (a).
7. method as claimed in claim 6, wherein this diamines with siloxane functional group accounts for 5～60 moles of % of all diamines.
8. method as claimed in claim 7, wherein this diamines with siloxane functional group is to be selected from by 1, two (the 3-aminocarbonyl propyls)-1 of 3-, 1,3,3-tetramethyl disiloxane (DSI), 1, two (the 4-amido butyl)-1,1,3 of 3-, the 3-tetramethyl disiloxane, 1, two (the 3-aminocarbonyl propyls)-1 of 3-, 3-dimethyl-1,3-diphenyl disiloxane, 1, two (the 3-aminocarbonyl phenyls)-1,1 of 3-, 3, the 3-tetramethyl disiloxane, 1, two (the 4-aminocarbonyl phenyls)-1,1 of 3-, 3, the 3-tetramethyl disiloxane, 1, two (the 3-amido phenoxymethyls)-1,1 of 3-, 3,3-tetramethyl disiloxane and 1, two (the 4-amido phenoxymethyls)-1,1 of 3-, 3, the cohort that the 3-tetramethyl disiloxane is formed at least a.
9. solubility light-sensitive polyimide resin combination, it comprises (A) water soluble light-sensitive polyimide polymer with recurring unit of formula (I) as claimed in claim 1; (B) (methyl) acrylic monomers thinning agent; And (C) light initiator; Composition (A) wherein: the part by weight of composition (B) is 100: 10～200, and the light initiator of composition (C), and during as 100 weight %, its contained ratio is 0.1～15.0 weight % with composition (A).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103261278A (en) * | 2011-01-07 | 2013-08-21 | 东丽株式会社 | Polyamic acid resin composition and method of producing the same |
| CN105906813A (en) * | 2016-06-05 | 2016-08-31 | 吉林大学 | Method for preparing regular block copolymerization polyimide siloxane single-layer film |
| CN113219796A (en) * | 2020-01-21 | 2021-08-06 | 新应材股份有限公司 | Removing method, laminate, forming method, polyimide resin, and stripping liquid |
-
2009
- 2009-01-09 CN CN200910001495A patent/CN101776847A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103261278A (en) * | 2011-01-07 | 2013-08-21 | 东丽株式会社 | Polyamic acid resin composition and method of producing the same |
| CN103261278B (en) * | 2011-01-07 | 2014-11-19 | 东丽株式会社 | Polyamic acid resin composition and method of producing the same |
| CN105906813A (en) * | 2016-06-05 | 2016-08-31 | 吉林大学 | Method for preparing regular block copolymerization polyimide siloxane single-layer film |
| CN113219796A (en) * | 2020-01-21 | 2021-08-06 | 新应材股份有限公司 | Removing method, laminate, forming method, polyimide resin, and stripping liquid |
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