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    • 专利摘要:
    When developing with aqueous alkali solution, it provides a positive photosensitive resin composition which does not reduce film | membrane, swelling, or peeling, gives a pattern with high dimensional stability after curing, and has low water absorption of a final cured film, and excellent alkali resistance. Formula (1) Wherein m is an integer of 3 or more and 10,000 or less, R 1 is a tetravalent organic group, R 2 is a divalent organic group, and 5 to 100 mol% of R 2 is a divalent organic group having fluorine. ) The positive photosensitive polyimide resin composition containing the organic solvent soluble polyimide which has a repeating unit shown by this, a polyamic acid, and the compound which generate | occur | produces an acid by light.
    公开号:KR20040044970A
    申请号:KR10-2004-7004117
    申请日:2002-09-18
    公开日:2004-05-31
    发明作者:나까야마도모나리；가또마사까즈；니히라다까야스
    申请人:닛산 가가쿠 고교 가부시키 가이샤；
    IPC主号:
    专利说明:

    Positive photosensitive polyimide resin composition {POSITIVE PHOTOSENSITIVE POLYIMIDE RESIN COMPOSITION}
    [2] As a polyimide positive type photosensitive resin composition, the thing which added the quinonediazide compound to the polyamic acid ester or polyimide which has an acidic group in a polyamic acid or a side chain is reported. However, since polyamic acid is so well dissolved in an alkaline developer, there is a problem such as a large film reduction during development, and therefore, an amine or the like must be added (USP. 4880722). On the other hand, polyimide (JP-A-3-115461) or polyamic acid ester (JP-A-64-60630) having an acidic group in the side chain is excellent in terms of resolution and the like, but is acidic in the polymer even after curing. Since the group remained, the absorption rate of the final cured film was high or the alkali resistance was highly likely to be significantly lowered. Moreover, in positive type photosensitive resin (Journal of Applied Polymer Science, Vol. 51, P. 1971-1978) which used the resin mixture of the polyamic acid ester and polyamic acid which has an acidic group as a detaching component, In order to convert into a mead, the curing at higher temperature is required and the film reduction after curing is also large.
    [3] Recently, the use of photosensitive insulating films including photosensitive polyimide resins has been expanded to extend not only to semiconductors but also to display fields. For this reason, excellent resolution without film reduction or swelling in fine pattern formation, which was not required in the conventional photosensitive polyimide resin, requires adhesion during development, dimensional stability of patterns in high temperature curing, and the like. Among them, Japanese Unexamined Patent Application Publication No. 2001-228609 discloses a positive photosensitive polyimide resin having excellent adhesion and developability composed of alkali-soluble polyimide, polyamic acid and o-quinonediazide compound. Depending on the combination, the whitening of the film and the water absorption of the final cured film may be problematic.
    [4] As described above, while the conventional positive photosensitive polyimide resin has excellent properties in each of them, developing a material having both lithographic properties and properties of the final cured film, and giving a pattern with low dimensional swelling and high dimensional stability, It was difficult.
    [5] The present invention has been made in view of the above circumstances, and when developed with an aqueous alkali solution, there is no film reduction, swelling or peeling and gives a pattern having high dimensional stability after curing, and has a low water absorption rate of the final cured film and excellent alkali resistance. It is to provide a photosensitive resin composition.
    [1] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to photosensitive materials suitable for surface protection films, interlayer insulating films, passivation films, electrode protection layers, etc. of electrical and electronic devices, in particular, semiconductor devices and display devices, and more particularly to positive photosensitive polyimide resin compositions that can be developed with aqueous alkali solutions. It is about.
    [6] (Initiation of invention)
    [7] MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors came to find out this invention.
    [8] That is, formula (1)
    [9]
    [10] Wherein m is an integer of 3 or more and 10,000 or less, R 1 is a tetravalent organic group, R 2 is a divalent organic group, and 5 to 100 mol% of R 2 is a divalent organic group having fluorine. )
    [11] An organic solvent soluble polyimide having a repeating unit represented by the formula (2)
    [12]
    [13] (Wherein n is an integer of 3 or more and 10000 or less, R 3 is a tetravalent organic group, and R 4 is a divalent organic group)
    [14] The polyamic acid which has a repeating unit shown by this, and the positive photosensitive polyimide resin composition characterized by containing the compound which generate | occur | produces an acid by light.
    [15] (The best mode for carrying out the invention)
    [16] The present invention will be described in detail below.
    [17] The composition of this invention contains the organic solvent soluble polyimide which has a repeating unit represented by the said General formula (1), the polyamic acid which has a repeating unit represented by the said General formula (2), and the compound which generate | occur | produces an acid by light. It is easy to etch by aqueous alkali solution, and can expose easily using the mask which has a predetermined pattern, and can obtain the polyimide resin coating film which has a fine and high dimensional accuracy relief pattern easily.
    [18] The method of obtaining the organic-solvent soluble polyimide which has a repeating unit represented by General formula (1) is not specifically limited.
    [19] Usually, it is obtained by reacting and polymerizing the organic tetracarboxylic acid or its derivative which comprises R <1> in General formula (1), and the organic diamine which comprises R <2> in General formula (1), Especially organic tetracarboxylic dianhydride (Hereinafter, abbreviated as acid anhydride) and organic diamine (hereinafter abbreviated as diamine) are reacted and polymerized, and it is common to make it a dehydration ring closure using a polyimide precursor.
    [20] The acid anhydride which comprises R <1> in General formula (1) is not specifically limited. Moreover, these may be used 1 type or in combination of 2 or more types.
    [21] If it dares to give an example, pyromellitic anhydride, 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride, 3,3', 4,4'- benzophenone tetracarboxylic dianhydride , 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfontetracarboxylic dianhydride, 2,2-bis (3,4 And aromatic tetracarboxylic anhydrides such as -dicarboxyphenyl) hexafluoroisopropylidene dianhydride. From the viewpoint of solubility, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-hexafluoro Isopropylidene diphthalic anhydride, 3,3 ', 4,4'- diphenylsulfontetracarboxylic dianhydride, etc. are preferable.
    [22] In addition, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4- Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclo Hexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentane acetic dianhydride, bicyclo [2.2.2] octo-7-ene-2,3,5,6 -Alicyclic tetracarboxylics such as tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3,5,6-tricarboxy-2-norbornane acetic dianhydride Aliphatic tetracarboxylic dianhydride such as acid dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride It can be given.
    [23] R <1> is a tetravalent organic group derived from tetracarboxylic acid in general formula (1), The structure is not specifically limited, These may be 1 type or 2 or more types may be mixed. Therefore, if the specific example is given, the tetravalent organic group (structure which removed two anhydride groups from tetracarboxylic dianhydride) which comprises said acid anhydride is mentioned.
    [24] In particular, in order to increase the solubility and the transparency of the solvent-soluble organic solvent of the polyimide resin having a repeating unit represented by the formula (1), when the four groups bonded to the R 1 are not bonded directly to the aromatic ring, or R 1 It is preferable when it is the tetravalent organic group which comprises the aromatic tetracarboxylic acid which has this fluorine. To obtain such a high solubility and transparency polyimide resin, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1 as an acid anhydride constituting R 1 in formula (1) , 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid Dianhydrides, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentane Acetic dianhydride, bicyclo [2.2.2] octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuranthtetracarboxylic dianhydride, To aromatic rings such as 3,5,6-tricarboxy-2-norbornane acetic anhydride The aromatic acid dianhydride containing fluorine such as isopropyl Li dendi phthalic anhydride is preferred as a dianhydride or 4,4'-hexafluoro composed of four carbonyl groups that are not bonded in contact. Similarly, the tetravalent organic group which comprises the said acid anhydride is mentioned also as a preferable specific example of R <1> .
    [25] The diamine which comprises R <2> in General formula (1) can be used 1 type or in combination of 2 or more, and if 5 mol% or more of the diamine component used is a diamine which has fluorine, it will not specifically limit. 5 to 100 mol% of R 2 is a diamine having a fluorine-containing polyimide obtained finally by using 5 to 100 mol% of the organic group is a divalent having fluorine. Fluorine has the effect of increasing the solubility of the organic solvent-soluble polyimide as well as the compatibility with polyamic acid, so that if the diamine component having fluorine is less than 5 mol%, that is, 5 mol% of R 2 having fluorine in the formula (1) If less, the compatibility with the polyamic acid is lowered and the solution becomes cloudy, or the cast film surface is whitened even if the solution is not cloudy. Especially, if 50-100 mol% of R <2> is a divalent organic group which has fluorine, it is preferable, and as a diamine to be used, it is preferable that 50-100 mol% is a diamine which has fluorine.
    [26] The fluorine in the diamine is generally introduced in the form of a fluoro group, a fluoroalkyl group or the like directly bonded to the benzene ring, and these may be singular or plural. Especially, from the viewpoint of compatibility with polyamic acid, the diamine which has a trifluoromethyl group and a hexafluoroisopropylidene group is preferable, The diamine which has a fluorine may be 1 type, or may be used in combination of 2 or more type.
    [27] If a specific example of the diamine having a trifluoromethyl group or a hexafluoroisopropylidene group is given, 2,2'-bis (trifluoromethyl) benzidine, 2,6,2 ', 6'-tetrakis (tri Fluoromethyl) benzidine, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-anilino) hexafluoropropane, 2,2-bis (3-anilino) hexafluoropropane, 2,2-bis (3-amino-4-toluyl) hexafluoro Propane and the like.
    [28] In the formula (1), R 2 is a divalent organic group derived from diamine, and the structure thereof is not particularly limited as long as 5 to 100 mol% of R 2 is a divalent organic group having fluorine. Moreover, 1 type of R <2> may be sufficient and 2 or more types may be mixed. And as R <2> which has fluorine, the divalent organic group which has a trifluoromethyl group and a hexafluoroisopropylidene group is preferable, and the specific example comprises the diamine which has the said trifluoromethyl group and the hexafluoroisopropylidene group. The divalent organic group (the structure remove | excluding two primary amino groups from diamine) is mentioned.
    [29] The diamine which comprises R <2> in General formula (1) can use diamine which does not have fluorine in 0-95 mol%, Preferably it is 0-50 mol%.
    [30] Examples of diamines that do not have fluorine include p-phenylenediamine, m-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl -1,4-phenylenediamine, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 3,3'-diaminodiphenylether, 4,4'-diaminodi Phenylsulfide, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-methylene-bis (2-methylaniline ), 4,4'-methylene-bis (2,6-dimethylaniline), 4,4'-methylene-bis (2,6-diethylaniline), 4,4'-methylene-bis (2-isopropyl -6-methylaniline), 4,4'-methylene-bis (2,6-diisopropylaniline), 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, benzidine, o-tolidine, m-tolidine, 3,3 ', 5,5'-tetramethylbenzidine, 2,2'-bis (trifluoromethyl) benzidine, 1,4-bis (4-aminophenoxy) Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) Benzene, bis [4- (4-aminophenoxy) phenyl] sulphone, bis [4- (3-aminophenoxy) phenyl] sulphone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane Aromatic diamines such as 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 1,6-hexanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4 -Bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexyl Aliphatic diamines, such as methane, are mentioned. The diamine which does not have these fluorine may be 1 type, or may be used in combination of 2 or more type.
    [31] As a specific example of R <2> which does not have a fluorine, the divalent organic group which comprises the said diamine which does not have a fluorine is mentioned. These can mix 1 type or 2 or more types in R <2> of General formula (1) in 0-95 mol%, Preferably it is 0-50 mol%.
    [32] In addition, R <2> of General formula (1) may have an acidic group, and this 1 type or 2 or more types may be mixed. Therefore, it is also possible to use the diamine which has an acidic group as the diamine which comprises R <2> in General formula (1). Examples of the acidic group include a phenolic hydroxyl group, a carboxylic acid, a sulfonamide group, and a sulfonic acid. The acidic groups of the positive photosensitive polymer are the most common carboxylic acid and phenolic hydroxyl groups. The organic solvent soluble polyimide which does not have an acidic group is insoluble in the alkaline developer, but the affinity for the alkaline developer is increased by introducing an acidic group, and if the acidic group is contained to some extent, dissolution in the alkaline developer of the film obtained from the organic solvent soluble polyimide By increasing speed, the developing time of the positive photosensitive polyimide resin composition of this invention can be shortened. However, since the acidic groups in the polyimide lower the film properties such as alkali resistance and hygroscopicity of the final cured film, R 2 having an acidic group in the formula (1) is preferably 10 mol% or less, in other words, 90 to 100 mol% of R 2 It is preferable that it is a divalent organic group which does not have an acidic group. Therefore, it is preferable that the diamine which has an acidic group in the diamine which comprises R <2> in General formula (1) is 10 mol% or less, and when it exceeds 10 mol%, the remaining acidic group will reduce film characteristics, such as alkali resistance and hygroscopicity of a final cured film. Let's do it.
    [33] The positive photosensitive polyimide resin composition of this invention makes it possible to obtain the high contrast of an exposure part and an unexposed part by combining the organic solvent soluble polyimide with low alkali affinity and the polyamic acid with very high alkali affinity. Therefore, the organic solvent soluble polyimide represented by the general formula (1) preferably has a dissolution rate of 0.1 μm / min or less in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 23 ° C., and when the dissolution rate is faster than 0.1 μm / min. Not only is the contrast lowered, but the sensitivity is also lowered.
    [34] The diamine having an acidic group contains a diamine having both fluorine and at the same time, and R 2 having an acidic group may be a divalent organic group having both an acidic group and a fluorine, but in this case, both the effect of having the fluorine and the effect of having an acidic group Exert.
    [35] Specific examples of diamine having an acidic group and R 2 include diamines having fluorine at the same time, such as 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4). -Amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3,5-dihydroxyphenyl) hexafluoropropane, 2,2-bis [4- (3-amino Diamines having phenolic hydroxyl groups such as -4-hydroxyphenoxy) phenyl] hexafluoropropane, and 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] hexafluoropropane The diamine which has a carboxyl group is mentioned, As R <2> which has an acidic group and fluorine simultaneously, the divalent organic group which comprises these diamines is mentioned, The diamine which has an acidic group and does not have a fluorine is 2, 4- diamino phenol, 3 , 5-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresolcinol, 2,5-diaminohydroquinone, bis (3-amino-4-hydroxyphenyl) ether, S (4-amino-3-hydroxyphenyl) ether, bis (4-amino-3,5-dihydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) methane, bis (4-amino 3-hydroxyphenyl) methane, bis (4-amino-3,5-dihydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxy Phenyl) sulfone, bis (4-amino-3,5-dihydroxyphenyl) sulfone, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3, 3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4'-bis ( 3-amino-4-hydroxyphenoxy) benzene, 1,3-bis (3-amino-4-hydroxyphenoxy) benzene, 1,4-bis (4-amino-3-hydroxyphenoxy) benzene , 1,3-bis (4-amino-3-hydroxyphenoxy) benzene, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] sulphone, bis [4- (3-amino-4 Diamine, 2,4-diamino benzo having phenolic hydroxyl groups such as -hydroxyphenoxy) phenyl] propane Acid, 2,5-diamino benzoic acid, 3,5-diamino benzoic acid, 4,6-diamino-1,3-benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic Acid, bis (4-amino-3-carboxyphenyl) ether, bis (4-amino-3,5-dicarboxyphenyl) ether, bis (4-amino-3-carboxyphenyl) sulfone, bis (4-amino- 3,5-dicarboxyphenyl) sulfone, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethyl Biphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethoxybiphenyl, 1,4-bis (4-amino-3-carboxyphenoxy) benzene, 1,3 -Bis (4-amino-3-carboxyphenoxy) benzene, bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone, bis [4- (4-amino-3-carboxyphenoxy) phenyl ] Diamine which has carboxyl groups, such as a propane, is mentioned, As R <2> which has an acidic group and does not have a fluorine, the divalent organic group which comprises these diamine is mentioned. The diamine which has these acidic groups may be one type, and may be used in combination of 2 or more type.
    [36] And from the viewpoint of the adhesiveness of the polyimide which is a final cured film, the polyimide which has a siloxane structure in R <2> of General formula (1) is preferable, and in order to obtain such a polyimide, to the diamine which comprises R <2> in General formula (1) Although siloxane containing diamine is also preferably used in combination, it is not limited to these. Moreover, it is preferable that R <2> which has a siloxane structure is 10 mol% or less from a viewpoint of the water absorptivity of a final cured film, and similarly, 10 mol% or less of the usage-amount of a siloxane containing diamine is also preferable.
    [37] As the siloxane-containing diamine, the formula (3)
    [38]
    [39] (Wherein R 5 represents a divalent organic group, R 6 represents a monovalent organic group, and k is an integer of 1 or more)
    [40] The siloxane containing diamine represented by is preferable.
    [41] As a preferable specific example of R <2> which has a siloxane structure, the divalent organic group which comprises the said siloxane containing diamine is mentioned.
    [42] The reaction of the acid anhydride with the diamine as a polyimide precursor is usually carried out in a polar solvent such as N-methylpyrrolidone, dimethylacetamide, γ-butyrolactone, and diglyme. The polar solvent used at this time will not be specifically limited if it melt | dissolves a polyimide precursor. The reaction temperature of tetracarboxylic dianhydride and diamine can select arbitrary temperature of -20-150 degreeC, Preferably -5-100 degreeC.
    [43] In order to convert a polyimide precursor into a polyimide, the polyimide precursor may be heated at 150 ° C. to 250 ° C. as it is, and azeotropically dehydrated by adding toluene or xylene to remove water generated in the dehydrating ring. Etc. are also possible.
    [44] In addition, catalyst imidization is a simpler method of converting a polyimide precursor into a polyimide. In this case, tertiary amines such as acetic anhydride, triethylamine, pyridine, isoquinoline, and imidazole can be added to the polyimide precursor solution and imidized at an arbitrary temperature of 0 ° C to 200 ° C. This method is known to be an effective method for converting polyamic acid into polyimide, because it does not require heating in particular and does not require complicated operations for removing water generated in the dehydrating ring. However, in the case of the polyimide resin containing a hydroxyl group, it is known that the hydroxyl group is reacted with acetic anhydride with high reactivity, so that this method cannot be employed.
    [45] In this invention, the repeating number m of the organic solvent soluble polyimide which has a repeating unit represented by General formula (1) is an integer of 3 or more and 10000 or less. When m is smaller than 3, the mechanical strength of the film formed from the composition obtained falls, and when m is larger than 10000, compatibility with polyamic acid falls extremely. Moreover, since the polyimide obtained by a normal polymerization reaction is an aggregate of molecules from which a polymerization degree differs, as an average value of the repeating number m of the organic solvent soluble polyimide which has a repeating unit represented by General formula (1) used for this invention, it is 10 1000 or more are preferable, More preferably, they are 15 or more and 100 or less.
    [46] The method of obtaining the polyamic acid which has a repeating unit represented by General formula (2) of this invention is not specifically limited.
    [47] Typically, the formula (2): R 3 organic acid dianhydride constituting a (referred to as an acid anhydride abbreviated) with an organic diamine (hereinafter referred to as diamine as abbreviated constituting the R 4 in the formula (2) ) Can be obtained by a method of reacting and polymerizing.
    [48] The acid anhydride which comprises R <3> in General formula (2) is not specifically limited. Moreover, these may be used 1 type or in combination of 2 or more types.
    [49] If it dares to give an example, pyromellitic anhydride, 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride, 3,3', 4,4'- benzophenone tetracarboxylic dianhydride , 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfontetracarboxylic dianhydride, 4,4'-hexafluoroiso And aromatic tetracarboxylic dianhydrides such as propylidene diphthalic anhydride.
    [50] In addition, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4- Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclo Hexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic dianhydride, bicyclo [2.2.2] octo-7-ene-2,3,5,6 -Alicyclic tetracarboxylics such as tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3,5,6-tricarboxy-2-norbornane acetic dianhydride Aliphatic tetracarboxylic dianhydrides such as acid dianhydrides, 1,2,3,4-butanetetracarboxylic dianhydrides Can be mentioned.
    [51] In general formula (2), R <3> is a tetravalent organic group derived from tetracarboxylic acid, The structure is not specifically limited, These may be 1 type or 2 or more types may be mixed. Therefore, if the specific example is given, the tetravalent organic group which comprises the acid anhydride mentioned above is mentioned.
    [52] The diamine which comprises R <4> in General formula (2) is not specifically limited. Moreover, these may be used 1 type or in combination of 2 or more types.
    [53] By all means, p-phenylenediamine, m-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4 -Phenylenediamine, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 3,3'-diaminodiphenylether, 4,4'-diaminodiphenylsulfide, 4,4'-diaminediphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-methylene-bis (2-methylaniline), 4,4 '-Methylene-bis (2,6-dimethylaniline), 4,4'-methylene-bis (2,6-diethylaniline), 4,4'-methylene-bis (2-isopropyl-6-methylaniline ), 4,4'-methylene-bis (2,6-diisopropylaniline), 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, benzidine, o-tolidine, m-tolidine, 3,3 ', 5,5'-tetramethylbenzidine, 2,2'-bis (trifluoromethyl) benzidine, 1,4-bis (4-aminophenoxy) benzene, 1,3 -Bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-amino Oxy] phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2, -bis [4- ( 3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-anilino) hexafluoropropane, 2, Aromatic diamine, such as 2-bis (3-anilino) hexafluoro propane and 2, 2-bis (3-amino-4- toluyl) hexafluoro propane, is mentioned.
    [54] 1,6-hexanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 4 And aliphatic diamines such as 4'-diaminodicyclohexyl methane and 4,4'-diamino-3,3'-dimethyldicyclohexyl methane.
    [55] In general formula (2), R <4> is a divalent organic group derived from diamine, The structure is not specifically limited, These may be 1 type or 2 or more types may be mixed. Therefore, if the specific example is given, the divalent organic group which comprises said diamine is mentioned.
    [56] And from the point of the adhesiveness of the polyimide which is a final cured film, the polyamic acid which has a siloxane structure in R <4> of General formula (2) is preferable, and in order to obtain such a polyimide, the diamine which comprises R <4> in General formula (2) Although siloxane containing diamine is also preferably used in combination, it is not limited to these. Moreover, it is preferable that R <4> which has a siloxane structure is 10 mol% or less from a viewpoint of the absorptivity of a final cured film, and likewise, 10 mol% or less of the usage-amount of a siloxane containing diamine is also preferable.
    [57] As the siloxane-containing diamine, the formula (3)
    [58] [Formula 3]
    [59]
    [60] (Wherein R 5 represents a divalent organic group, R 6 represents a monovalent organic group, and k is an integer of 1 or more)
    [61] The siloxane containing diamine represented by is preferable.
    [62] As a preferable specific example of R <4> which has a siloxane structure, the divalent organic group which comprises the said siloxane containing diamine is mentioned.
    [63] As described above, in the polyamic acid having a repeating unit represented by the formula (2), the structures of R 3 and R 4 are not particularly limited, but from the viewpoint of absorbency of the final cured film, at least one of R 3 or R 4 has fluorine. It is desirable to have. In order to obtain such a polyamic acid, an acid anhydride having fluorine may be used as the acid anhydride constituting R 3 in the formula (2), or a diamine having fluorine may be used as the diamine constituting R 4 in the formula (2). . Specific examples of the acid anhydride having fluorine include 4,4'-hexafluoroisopropylidenediphthalic anhydride. Examples of the diamine having fluorine include 2,2'-bis (trifluoromethyl) benzidine, 2,6,2 ', 6'-tetrakis (trifluoromethyl) benzidine, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-anilino) hexafluoropropane, 2,2-bis (3-anilino) hexafluoropropane, 2,2- Bis (3-amino-4-toluyl) hexafluoropropane and the like. Preferred examples of R 3 having fluorine include tetravalent organic groups constituting the acid anhydride having fluorine, and preferred examples of R 4 having fluorine include divalent organic groups constituting the diamine having fluorine. have.
    [64] Formula (2) The preferred content of R 4 and R 3 has a fluorine has a fluorine in a R 4 is a R 3 has a fluorine to the total R 3 has a fluorine for from 50 to 100 mol%, or all of R 4 50 to 100 mole%, or the total of the molar ratio of R 4 having fluorine on the molar ratio of R 3 and R 4 having a total fluorine to the total R 3 50~100 mol%. When the total of the molar ratio of R 4 having fluorine on the R 3 molar ratio and the total R 4 has a fluorine to the total R 3 larger than 100 mol% used as the coating solution deteriorates the wet property relative to a substrate, the uniformity of the coating film The adhesiveness to a castle and a board | substrate worsens.
    [65] The reaction for obtaining a polyamic acid from an acid anhydride and a diamine is usually carried out in a polar solvent such as N-methylpyrrolidone, dimethylacetamide, γ-butyrolactone, and diglyme. The polar solvent used at this time will not be specifically limited if it melt | dissolves a polyimide precursor. The reaction temperature of tetracarboxylic dianhydride and diamine can select arbitrary temperature of -20-150 degreeC, Preferably -5-100 degreeC.
    [66] In this invention, the repeating number n of the polyamic acid which has a repeating unit represented by General formula (2) is an integer of 3 or more and 10000 or less. When n is smaller than 3, the mechanical strength of the film formed from the composition obtained falls, and when n is larger than 10000, compatibility with a solvent-soluble polyimide falls extremely. Moreover, since the polyimide obtained by a normal polymerization reaction is an aggregate of molecules from which a polymerization degree differs, as an average value of the repeating number m of the organic solvent soluble polyimide which has a repeating unit represented by General formula (2) used for this invention, it is 10 1000 or more are preferable, More preferably, they are 15 or more and 100 or less.
    [67] The compound which generate | occur | produces an acid by the light of this invention will not be specifically limited if it has a function which produces | generates an acid by photoreaction and improves the solubility to the alkaline developing solution of a light irradiation part. Moreover, these may be used 1 type or in combination of 2 or more types.
    [68] If the specific example is given, o-quinone diazide compound, allyl diazonium salt, diallyl iodonium salt, triallyl sulfonium salt, o-nitrobenzyl ester, p-nitrobenzyl ester, trihalomethyl group substitution s-tree Azine derivatives, imidesulfonate derivatives, and the like. Moreover, a sensitizer can be used together as needed. Examples of the sensitizer include perylene, anthracene, thioxanthone, Michler's ketone, benzophenone, fluorene and the like.
    [69] Among the compounds which generate an acid by these lights, an o-quinonediazide compound is preferable in view of sensitivity and resolution.
    [70] Usually, the o-quinonediazide compound is o-quinonediazide sulfonic acid ester or o-quinonediazide obtained by condensation of o-quinonediazide sulfonyl chloride with a compound having a hydroxyl group or a compound having an amino group in the presence of a basic catalyst. Used as sulfonamide.
    [71] As o-quinone diazide sulfonic-acid component which comprises the said o-quinone diazide sulfonyl chloride, for example, 1, 2- naphthoquinone- 2-diazide- 4-sulfonic acid, a 1, 2- naphthoquinone- 2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2- diazide-6-sulfonic acid, etc. are mentioned.
    [72] Examples of the compound having a hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, 4,4-isopropylidenediphenol, and 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxyphenylsulfone, 4,4-hexafluoroisopropylidenediphenyl, 4,4 ', 4 "-trihydroxytriphenylmethane, 1 , 1,1-tris (4-hydroxyphenyl) ethane, 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 2 , 4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzo Phenolic compounds such as phenone, 2,3,4,2 ', 4'-pentahydroxybenzophenone, ethanol, 2-propanol, 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene Glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, butyl lactate Aliphatic alcohols, such as these, are mentioned.
    [73] Moreover, aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4 Aniline, such as "-diamino diphenylmethane and 4,4"-diamino diphenyl ether, and aminocyclohexane are mentioned.
    [74] Moreover, as a compound which has both a hydroxyl group and an amino group, for example, o-aminophenol, m-aminophenol, p-aminophenol, 4-amino resorcinol, 2, 3- diamino phenol, 2, 4- Diaminophenol, 4,4'-diamino-4 "-hydroxytriphenylmethane, 4-amino-4 ', 4" -dihydroxytriphenylmethane, bis (4-amino-3-carboxy-5- Hydroxyphenyl) ether, bis (4-amino-3-carboxy-5-hydroxyphenyl) methane, bis (4-amino-3-carboxy-5-hydroxyphenyl) sulfone, 2,2, -bis (4 Aminophenols such as -amino-3-carboxy-5-hydroxyphenyl) propane, 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) hexafluoropropane, 2-aminoethanol, 3 Alkanolamines, such as -aminopropanol and 4-aminocyclohexanol, are mentioned.
    [75] Usually, it is common to use part or all of the hydroxyl group or the amino group of these compounds by substituting or reacting with the above orthoquinonediazidesulfonic acid group, and using two substituents, three substituents, four substituents and five substituents alone or as a mixture thereof.
    [76] In the positive photosensitive polyimide resin composition of the present invention, the amount of the organic solvent-soluble polyimide having a repeating unit represented by the general formula (1) and the polyamic acid having the repeating unit represented by the general formula (2) is sensitive, resolution, and development. It is preferable that the latter is 5-400 weight part with respect to 100 weight part of electrons from a viewpoint of sex. When polyamic acid is less than 5 weight part with respect to 100 weight part of organic solvent soluble polyimides, developability of the light irradiation part of a positive photosensitive resin composition film | membrane will become insufficient, and the contrast of a light irradiation part and an unirradiation part will become small, and a sensitivity will also fall. On the other hand, when polyamic acid exceeds 400 weight part with respect to 100 weight part of organic solvent soluble polyimides, the developing solution resistance of the light irradiation part of a positive photosensitive resin composition film | membrane will fall extremely, and the film | membrane reduction of a post-development pattern will become large and resolution will also fall. do. Especially, it is especially preferable that a polyamic acid is 50-200 weight part with respect to 100 weight part of organic solvent soluble polyimides.
    [77] In consideration of the sensitivity, resolution, and post-firing film properties of the positive photosensitive polyimide resin composition, a compound which generates an acid by light is 1 to 100 parts by weight based on 100 parts by weight of the total amount of the organic solvent-soluble polyimide and polyamic acid. 50 parts by weight is preferred. When the compound which produces | generates an acid with light with respect to 100 weight part of total amounts of an organic solvent soluble polyimide and a polyamic acid is less than 1 weight part, since the solubility to the alkali developing solution of the light-irradiating part of a positive photosensitive resin composition film is insufficient, The contrast of the irradiated portion and the unirradiated portion is reduced. On the other hand, when the compound which produces | generates an acid by light with respect to 100 weight part of total amounts of organic solvent soluble polyimide and a polyamic acid exceeds 50 weight part, the mechanical characteristic of the cured film obtained by processing a positive photosensitive resin composition film at high temperature will fall. do. Especially, it is preferable that the compound which generate | occur | produces an acid by light is 10-40 weight part with respect to 100 weight part of total amounts of an organic solvent soluble polyimide and a polyamic acid.
    [78] The positive photosensitive polyimide resin composition of this invention is used as a solution melt | dissolved in the organic solvent, when used for electrical and electronic devices. This organic solvent will not be specifically limited if polyimide, polyamic acid, and the compound which generate | occur | produce an acid by light uniformly, and these components are compatible. Specific examples thereof include, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide and γ-butyro. Lactone, cyclohexanone, etc. are mentioned.
    [79] In addition, you may mix and use other organic solvent, as long as this composition is melt | dissolved uniformly according to the objective. Specific examples of such organic solvents include 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxyethyl acetate, 2-methoxy-1-propanol, 3-methoxypropyl acetate, and lactic acid. Ethyl, butyl lactate, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, butyl carbitol acetate, ethylene glycol and the like.
    [80] The method of obtaining the solution of the positive photosensitive polyimide resin composition of this invention is a polyamide which has a repeating unit represented by General formula (2) to the solution which reacted and polymerized the organic-solvent soluble polyimide which has a repeating unit represented by General formula (1). The organic solvent soluble polyimide resin which has the repeating unit represented by General formula (1) which may dissolve the compound which generate | occur | produces an acid by acid solution and light, and precipitated and recovered using the poor solvent, The repeating unit represented by General formula (2) The polyamic acid having a compound may be dissolved in the organic solvent together with a compound which generates an acid by light.
    [81] The density | concentration of the said resin composition solution is not specifically limited as long as each component is melt | dissolving uniformly. Usually, it is generally used in the range of 1-50 weight%, Especially preferably, 5-30 weight% from the ease of a process surface.
    [82] The positive photosensitive polyimide resin composition of this invention can contain an organosilane compound and an aluminum chelate compound in order to improve adhesiveness with the board | substrate of a hardened film.
    [83] As an organosilane compound, vinyl triethoxysilane, 3-glycidoxy propyl triethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-aminopropyl triethoxysilane, etc. are mentioned, for example. . As an aluminum chelate compound, tris (acetylacetonate) aluminum, acetyl acetate aluminum diisopropylate, etc. are mentioned, for example.
    [84] The solution of the positive photosensitive polyimide resin composition of the present invention can be spin-coated on a substrate such as a silicon wafer, an oxide film, or a nitride film, and then preliminarily dried at 80 to 130 ° C. to form a film.
    [85] By mounting a mask having a predetermined pattern on the film to irradiate light and developing with an alkaline developer, an exposed portion is washed away to obtain a relief pattern having a sharp end surface. The developer used at this time may be any aqueous alkali solution, and may be an aqueous solution of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline and the like. Amine aqueous solutions, such as aqueous solution, ethanolamine, propylamine, and ethylenediamine, are mentioned.
    [86] The alkali developer is generally 10% by weight or less of an aqueous solution, and preferably 0.5 to 3.0% by weight of an aqueous solution or the like is used. Moreover, alcohol and surfactant can also be added and used to the said developing solution. These are each mix | blended in 0.05-10 weight part with respect to 100 weight part of developing solutions, respectively.
    [87] The present composition has high solubility in the exposed portion, and the development can be easily performed at room temperature.
    [88] By heat-processing the board | substrate which has the obtained relief pattern at 180-400 degreeC, the polyimide coating film which is excellent in heat resistance, chemical-resistance, and electrical characteristics, and has a favorable relief pattern can be obtained.
    [89] The composition of the present invention has a high sensitivity and high resolution positive photosensitive characteristics, and is easily etched by an aqueous alkali solution, and is exposed to light using a mask having a predetermined pattern, thereby forming a polyimide having a fine shape and a relief pattern with high dimensional accuracy. A resin coating film can be obtained easily.
    [90] The positive photosensitive polyimide resin composition of the present invention can be used for interlayer insulating films, passivation films, buffer coating films, multilayer printed circuit board insulating films, etc. of semiconductor devices, but also for protective films of thin film transistors of liquid crystal display devices and electrodes of organic EL devices. It can also be used for a protective film.
    [91] Although an Example is given to the following and this invention is demonstrated in more detail, this invention is not limited to these.
    [92] Synthesis Example 1
    [93] Synthesis of Organic Solvent Soluble Polyimide (1)
    [94] 2,2'-bis (3-amino-4-toluyl) hexafluoropropane (hereinafter abbreviated as BIS-AT-AF) 16.30 g (0.045 mol), 3,5-diaminobenzoic acid (hereinafter DABA) D) 0.76 g (0.005 mole) and cyclobutanetetracarboxylic dianhydride (hereinafter abbreviated CBDA) 9.81 g (0.050 mole) to N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) ) Was dissolved in 62.70 g and reacted at room temperature for 24 hours.
    [95] NMP 246.30g, acetic anhydride 51.05g (0.500mol), and pyridine 39.55g (0.300mol) were added to the reaction solution, and it carried out dehydration ring reaction at 40 degreeC for 3 hours. The solution was poured into pure water, filtered and dried to obtain 23.70 g of a powdered organic solvent soluble polyimide (1) having a number average molecular weight of 26,100 (average of repeating units was about 49) in terms of polyethylene oxide.
    [96] The polyimide (1) was dissolved in NMP, applied directly onto a silicon wafer using a spin coater, and heated at 120 ° C. for 2 minutes on a hot plate to obtain a coating film having a thickness of about 2.0 μm. This coating film was immersed in 23 degreeC 2.38 weight% tetramethylammonium hydroxide aqueous solution (TMAH) for 60 to 180 second, and the dissolution rate was measured and found to be 0.06 micrometer / min.
    [97] Synthesis Example 2
    [98] Synthesis of Organic Solvent Soluble Polyimide (2)
    [99] BIS-AT-AF 15.76 g (0.044 mol), DABA 0.61 g (0.004 mol), bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane (hereinafter abbreviated as APDS) 0.62 g (0.002 mol) and 9.81 g (0.050 mol) of CBDA were dissolved in 62.53 g of NMP and reacted at room temperature for 24 hours.
    [100] NMP 245.67g, acetic anhydride 51.05g (0.500mol), and pyridine 39.55g (0.300mol) were added to the reaction solution, and it carried out dehydration ring reaction at 40 degreeC for 3 hours. The solution was poured into pure water, filtered and dried to obtain 27.55 g of a powdered organic solvent-soluble polyimide (2) having a number average molecular weight of 21,200 (the average of a repeating unit was about 40) in terms of polyethylene oxide. The dissolution rate of the polyimide (2) was measured in the same manner as in Synthesis example 1 and was 0.05 µm / min.
    [101] Synthesis Example 3
    [102] Synthesis of Organic Solvent Soluble Polyimide (3)
    [103] 18.12 g (0.050 mol) of BIS-AT-AF and 9.81 g (0.050 mol) of CBDA were dissolved in 65.17 g of NMP and allowed to react at room temperature for 24 hours.
    [104] NMP256.03g, acetic anhydride 51.05g (0.500mol), and pyridine 39.55g (0.300mol) were added to the reaction solution, and dehydration ring reaction was carried out at 40 degreeC for 3 hours. The solution was poured into pure water, filtered and dried to obtain 23.18 g of a powdered organic solvent-soluble polyimide (3) having a number average molecular weight of 26,000 (average of repeating units was about 47). The dissolution rate of the polyimide (3) was measured in the same manner as in Synthesis example 1 and found to be 0.00 µm / min.
    [105] Synthesis Example 4
    [106] Synthesis of Organic Solvent Soluble Polyimide (4)
    [107] 2,2'-bis (trifluoromethyl) benzidine (hereinafter abbreviated as TFMB) 16.01 g (0.050 mol) and 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene 13.21 g (0.050 mol) of -1,2-dicarboxylic dianhydride was dissolved in 68.18 g of NMP and reacted at room temperature for 36 hours.
    [108] NMP267.85g, acetic anhydride 51.05g (0.500mol), and pyridine 39.55g (0.300mol) were added to the reaction solution, and dehydration ring reaction was carried out at 40 degreeC for 3 hours. The solution was poured into pure water, filtered and dried to obtain 26.30 g of a powdered organic solvent-soluble polyimide (4) having a number average molecular weight of 15,900 (the average of the repeating units was about 27) in terms of polyethylene oxide. The dissolution rate of the polyimide (4) was measured in the same manner as in Synthesis example 1 and found to be 0.00 µm / min.
    [109] Synthesis Example 5
    [110] Synthesis of Organic Solvent Soluble Polyimide (5)
    [111] 15.14 g (0.035 mol) of bis [4- (3-aminophenoxy) phenyl] sulfone, 2.28 g (0.015 mol) of DABA, and 9.61 g (0.049 mol) of CBDA were reacted for 6 hours at room temperature in 153.17 g of NMP.
    [112] NMP 157.67g, acetic anhydride 51.05g (0.500mol), and pyridine 39.55g (0.300mol) were added to the reaction solution, and dehydration ring reaction was carried out at 40 degreeC for 3 hours. The solution was poured into pure water, filtered and dried to obtain 24.33 g of a powdered organic solvent-soluble polyimide (5) having a number average molecular weight of 36,000 (average of repeating units was about 66) in terms of polyethylene oxide. It was 0.20 micrometer / min when the dissolution rate of the polyimide (5) was measured similarly to the synthesis example 1.
    [113] Synthesis Example 6
    [114] Preparation of polyamic acid solution (6)
    [115] 15.21 g of TFMB, 0.62 g of APDS, and 14.42 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (hereinafter abbreviated as BPDA) were reacted for 12 hours at room temperature in 171.41 g of NMP to give a polyamic acid. The NMP solution of (6) was obtained. The number average molecular weight was 19,500 in terms of polyethylene oxide (average of repeating units was about 32).
    [116] Synthesis Example 7
    [117] Preparation of polyamic acid solution (7)
    [118] 15.21 g of TFMB, 0.62 g of APDS, 6.99 g of BPDA, and 5.18 g of pyromellitic anhydride (hereinafter abbreviated as PMDA) were reacted for 12 hours at room temperature in 158.67 g of NMP to obtain an NMP solution of polyamic acid (7). The number average molecular weight was 20,500 in terms of polyethylene oxide (average of repeating units was about 36).
    [119] Synthesis Example 8
    [120] Preparation of polyamic acid solution (8)
    [121] 15.21 g of TFMB, 0.62 g of APDS, and 10.14 g of PMDA were reacted for 12 hours at room temperature in 147.16 g of NMP to obtain an NMP solution of polyamic acid (8). The number average molecular weight was 19,500 in terms of polyethylene oxide (average of repeating units was about 36).
    [122] Synthesis Example 9
    [123] Preparation of polyamic acid solution (9)
    [124] 9.41 g of 4,4-diaminodiphenylmethane (hereinafter abbreviated as DDM), 21.32 g of APDS 0.62 g, 4,4'-hexafluoroisopropylidenediphthalic anhydride (hereinafter abbreviated as 6FDA) NMP It reacted at room temperature in 177.65g for 12 hours, and obtained the NMP solution of polyamic acid (9). The number average molecular weight was 19,000 in terms of polyethylene oxide (average of repeating units was about 29).
    [125] Example 1
    [126] 1.80 g of a solvent-soluble polyimide resin (1) was dissolved in a mixed solvent of 7.83 g of ethyl lactate (hereinafter abbreviated as EL) and 11.47 g of NMP, and 8.00 g of a polyamic acid solution (6) was added to the mixed solution. 1 mol of 4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] and 1,2-naphthoquinone-2-diazide-5-sulfonyl 0.90 g of a photosensitive agent (manufactured by Toyo Chemical Co., Ltd., P-200) synthesized by a condensation reaction of 2 mol of chloride was added thereto, stirred at room temperature for 1 hour, and filtered through a 0.2 µm filter to obtain a positive photosensitive polyimide resin composition. A solution was obtained.
    [127] This solution was directly applied onto a silicon wafer using a spin coater and heated at 120 ° C. for 2 minutes on a hot plate to obtain a coating film having a thickness of about 1.0 μm. Ultraviolet light was irradiated to this coating film by Canon ultraviolet irradiation device PLA-501 for 15 second through the test mask. After exposure, the solution was immersed in a 2.38% TMAH aqueous solution (manufactured by Tokyooka Co., Ltd., NMD-3) at 23 ° C. for 45 seconds to develop. After development, the film thickness was about 1.0 mu m and no film reduction was observed. Pattern resolution was formed up to 3 μm in line / space without pattern stripping.
    [128] When the pattern was heated at 250 ° C. for 30 minutes in a circular drying furnace, the remaining film thickness ratio was 80% and the pattern shape change was hardly seen.
    [129] Moreover, the photosensitive polyimide resin composition coating film formed on the silicon wafer similarly to the above was immersed for 24 hours in the pure water maintained at 23 degreeC after high temperature heating in the 250 degreeC 30 minute circulation drying furnace. This coating film was measured by McScience thermogravimetric analyzer TG-DTA, and the water absorption of the coating film was 2.2%.
    [130] Example 2
    [131] A solution of the positive photosensitive polyimide resin composition was obtained in the same manner as in Example 1 except that the solvent-soluble polyimide resin (1) was changed to a solvent-soluble polyimide resin (2).
    [132] This solution was directly applied onto a silicon wafer using a spin coater and heated at 120 ° C. for 2 minutes on a hot plate to obtain a coating film having a thickness of about 1.0 μm. Ultraviolet light was irradiated to this coating film with PLA-501 for 15 second through the test mask. It developed by immersing for 40 second in 23 degreeC NMD-3 after exposure. After development, the film thickness was about 1.0 mu m and no film reduction was observed. Pattern resolution was formed up to 3 μm in line / space without pattern stripping.
    [133] When the pattern was heated at 250 ° C. for 30 minutes in a circulation drying furnace, the remaining film thickness ratio was 80% and the pattern shape change was a practical level. Moreover, the water absorption was measured like Example 1 and found to be 1.7%.
    [134] Example 3
    [135] A solution of the positive photosensitive polyimide resin composition was obtained in the same manner as in Example 1 except that the polyamic acid solution (6) was changed to the polyamic acid solution (9).
    [136] This photosensitive polyimide solution was directly applied onto a silicon wafer using a spin coater and heated at 120 ° C. for 2 minutes on a hot plate to obtain a coating film having a thickness of about 1.0 μm. Ultraviolet light was irradiated to this coating film with PLA-501 for 15 second through the test mask. It developed by immersing in 23 degreeC NMD-3 for 60 second after exposure. After development, the film thickness was about 1.0 mu m and no film reduction was observed. Pattern resolution was formed up to 5 μm in line / space without pattern stripping.
    [137] When the pattern was heated at 250 ° C. for 30 minutes in a circulation drying furnace, the remaining film thickness ratio was 82% and the pattern shape change was a practical level. Moreover, it was 1.9% when the water absorption rate was measured like Example 1.
    [138] Example 4
    [139] Positive type photosensitive polyimide similarly to Example 1 except having changed the solvent soluble polyimide resin (1) into the solvent soluble polyimide resin (3), and the polyamic acid solution (6) into the polyamic acid solution (7). The solution of the resin composition was obtained.
    [140] This photosensitive polyimide solution was directly applied onto a silicon wafer using a spin coater and heated at 120 ° C. for 2 minutes on a hot plate to obtain a coating film having a thickness of about 1.0 μm. Ultraviolet light was irradiated to this coating film with PLA-501 for 15 second through the test mask. It developed by immersing in 23 degreeC NMD-3 for 60 second after exposure. After development, the film thickness was about 1.0 mu m and no film reduction was observed. Pattern resolution was formed up to 3 μm in line / space without pattern stripping.
    [141] When the pattern was heated at 250 ° C. for 30 minutes in a circulation drying furnace, the remaining film thickness ratio was 80% and the pattern shape change was a practical level. Moreover, it was 1.4% when the water absorption rate was measured similarly to Example 1.
    [142] Example 5
    [143] 1.20 g of solvent-soluble polyimide resin (4) was dissolved in a mixed solvent of EL 7.83 g and NMP 7.47 g, and then 12.00 g of polyamic acid solution (8) was added, and 0.90 g of P-200 was added to the mixed solution. After stirring for 1 hour, the solution was filtered through a 0.2 μm filter to obtain a solution of the positive photosensitive polyimide resin composition.
    [144] This photosensitive polyimide solution was directly applied onto a silicon wafer using a spin coater and heated at 120 ° C. for 2 minutes on a hot plate to obtain a coating film having a thickness of about 1.0 μm. Ultraviolet light was irradiated to this coating film with PLA-501 for 15 second through the test mask. It developed by immersing in 23 degreeC NMD-3 for 60 second after exposure. After development, the film thickness was about 1.0 mu m and no film reduction was observed. Pattern resolution was formed up to 5 μm in line / space without pattern stripping.
    [145] When the pattern was heated at 250 ° C. for 30 minutes in a circular drying furnace, the remaining film thickness ratio was 78% and the pattern shape change was a practical level. Moreover, the water absorption was measured in the same manner as in Example 1 and found to be 0.8%.
    [146] Comparative Example 1
    [147] 3 g of solvent-soluble polyimide resin (2) was added to a mixed solution of 7.83 g of EL and 18.27 g of NMP, and 0.90 g of P-200 was added to the mixed solution and stirred at room temperature for 1 hour, followed by filtration with a 0.2 µm filter. A solution of the type photosensitive composition was obtained.
    [148] This photosensitive polyimide solution was directly applied onto a silicon wafer using a spin coater, and heated at 120 ° C. for 3 minutes on a hot plate to obtain a coating film having a thickness of about 1.0 μm. Ultraviolet light was irradiated to this coating film with PLA-501 for 15 second through the test mask. After exposure, the film was immersed in NMD-3 at 23 ° C. for 180 seconds and developed. However, a residual film was observed in the exposed portion to obtain a pattern. Moreover, it was 1.9% when the water absorption was measured by the method similar to Example 1.
    [149] Comparative Example 2
    [150] 0.90 g of P-200 was added to a mixed solution of 7.83 g of EL and 1.27 g of NMP in 20.00 g of the polyamic acid solution (6), stirred at room temperature for 1 hour, and filtered through a 0.2 µm filter to form a positive photosensitive resin composition. A solution of was obtained.
    [151] This photosensitive polyimide solution was directly applied onto a silicon wafer using a spin coater and heated at 120 ° C. for 2 minutes on a hot plate to obtain a coating film having a thickness of about 1.0 μm. Ultraviolet light was irradiated to this coating film with PLA-501 for 15 second through the test mask. After exposure, it developed by immersing in 23 degreeC NMD-3 for 20 second, but the unexposed part melt | dissolved and rolled, and the pattern was not obtained. Moreover, it was 0.8% when the water absorption was measured by the method similar to Example 1.
    [152] Comparative Example 3
    [153] 3 mol of solvent-soluble polyimide resin (5) was added to 17.55 g of γ-butyrolactone and 17.55 g of NMP mixed solvent, and 1 mol of 2,3,4,4'-tetrahydroxybenzophenone and 1,2- 0.90 g of a photosensitive agent (4NT-300, manufactured by Toyo Chemical Co., Ltd.) synthesized by condensation of 3 mol of naphthoquinone-2-diazide-5-sulfonyl chloride was added thereto, stirred at room temperature for 1 hour, and then 0.2 µm It filtered by the filter and obtained the solution of positive type photosensitive resin composition.
    [154] This photosensitive polyimide solution was directly applied onto a silicon wafer using a spin coater, and heated at 120 ° C. for 3 minutes on a hot plate to obtain a coating film having a thickness of about 1.0 μm. Ultraviolet light was irradiated to this coating film with PLA-501 through a test mask for 35 second. It developed by immersing in NMD-3 of 23 degreeC after exposure for 150 second. The film thickness after development was about 0.97 mu m and the film decrease was slight. However, pattern peeling was observed at 30 μm or less in the line / space.
    [155] When the pattern was heated at 250 ° C. for 30 minutes in a circulation drying furnace, the remaining film thickness ratio was 82% and the pattern shape change was a practical level. Moreover, when water absorption was measured like Example 1, it was 3% or more.
    [156] Comparative Example 4
    [157] 1.80 g of a solvent-soluble polyimide resin (5) was dissolved in a mixed solvent of 7.55 g of γ-butyrolactone and 10.75 g of NMP, and 8.00 g of a polyamic acid solution (6) was further added, and 0.90 g of P-200 was added to the mixed solution. The mixture was stirred at room temperature for 1 hour, and then filtered through a 0.2 µm filter to obtain a solution of the positive photosensitive polyimide resin composition.
    [158] The photosensitive polyimide solution was directly applied onto a silicon wafer using a spin coater and heated at 120 ° C. for 3 minutes on a hot plate, whereby only a non-uniform surface and a cloudy appearance were obtained.
    [159] Polyimide Component% By weightPolyamic Acid Component% By weightPhotosensitizer *ExampleOne(One)60(6)40P-200 2(2)60(6)40P-200 3(One)60(9)40P-200 4(3)60(7)40P-200 5(4)40(8)60P-200 Comparative exampleOne(2)100-0P-200 2-0(6)100P-200 3(5)100-04NT-300 4(5)60(6)40P-200 * Photosensitizer is added 30 parts by weight to 100 parts by weight of polyimide and polyamic acid
    [160] Exposure time (seconds)Developing time (second)Post-development film thickness (㎛)Resolution (μm)Absorption rate (%) ExampleOne15451.032.2 215401.031.7 315601.031.9 415601.031.4 515601.050.8 Comparative exampleOne40> 1801.0Remnant1.9 21500-0.8 3351500.97> 30> 3 4A uniform coating film was not obtained.
    [161] According to the present invention, when developing with an aqueous alkali solution, a positive photosensitive resin composition can be obtained which is free from film reduction, swelling and peeling, gives a pattern with high dimensional stability after curing, has low absorption of the final cured film, and is excellent in alkali resistance. .
    [162] The positive photosensitive polyimide resin composition of the present invention can be used not only for interlayer insulating films, passivation films, buffer coat films, multilayer printed circuit board insulating films, etc., but also for protective films of thin film transistors of liquid crystal display devices, electrode protective films of organic EL devices, and the like. Is preferred.
    权利要求:
    Claims (8)
    [1" claim-type="Currently amended] Formula (1)

    Wherein m is an integer of 3 or more and 10,000 or less, R 1 is a tetravalent organic group, R 2 is a divalent organic group, and 5 to 100 mol% of R 2 is a divalent organic group having fluorine. )
    An organic solvent soluble polyimide having a repeating unit represented by the formula (2)

    (Wherein n is an integer of 3 or more and 10000 or less, R 3 is a tetravalent organic group, and R 4 is a divalent organic group)
    The positive photosensitive polyimide resin composition containing the polyamic acid which has a repeating unit shown by this, and the compound which generate | occur | produces an acid by light.
    [2" claim-type="Currently amended] The positive photosensitive polyimide resin composition according to claim 1, wherein in the solvent-soluble polyimide having a repeating unit represented by the formula (1), 90 to 100 mol% of R 2 is a divalent organic group having no acidic group.
    [3" claim-type="Currently amended] The solvent-soluble polyimide of Claim 1 or 2 whose solvent-soluble polyimide which has a repeating unit represented by General formula (1) is 0.1 micrometer / min or less in the 23 degreeC 2.38 weight% tetramethylammonium hydroxide aqueous solution. The positive photosensitive polyimide resin composition which is a mid.
    [4" claim-type="Currently amended] The solvent-soluble polyimide resin according to any one of claims 1 to 3, wherein in the solvent-soluble polyimide resin having the repeating unit represented by the formula (1), four carbonyl groups bonded to R 1 do not directly bond to the aromatic ring, or R tetravalent organic group positive photosensitive polyimide resin composition 1, the configuration of an aromatic tetracarboxylic acid having fluorine.
    [5" claim-type="Currently amended] The polyamic acid according to any one of claims 1 to 4, wherein the polyamic acid having a repeating unit represented by the general formula (2) is 10 to about 100 parts by weight of the solvent-soluble polyimide resin having the repeating unit represented by the general formula (1). Positive type photosensitive containing 400 weight part and containing 1-50 weight part of compounds which generate | occur | produce an acid by light with respect to 100 weight part of total amounts of the repeating unit represented by General formula (1) and the repeating unit represented by General formula (2) Polyimide resin composition.
    [6" claim-type="Currently amended] The compound for generating an acid by light according to any one of claims 1 to 5 is 1,2-naphthoquinone diazide-4-sulfonic acid ester, 1,2-naphthoquinone diazide-5- Sulfonic acid esters, 1,2-naphthoquinonediazide-6-sulfonic acid esters, 1,2-naphthoquinonediazide-4-sulfonamides, 1,2-naphthoquinonediazide-5-sulfonamides and 1, Positive type photosensitive polyimide resin composition which is at least 1 sort (s) of compound chosen from the group which consists of 2-naphthoquinone diazide-6-sulfonamide.
    [7" claim-type="Currently amended] The solution which melt | dissolved the positive photosensitive polyimide resin composition in any one of Claims 1-6 in the organic solvent so that it may become 1-50 weight% of concentration.
    [8" claim-type="Currently amended] The cured film which apply | coated and dried the solution of Claim 7 on a base material.
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    同族专利:
    公开号 | 公开日
    US20040197699A1|2004-10-07|
    US7026080B2|2006-04-11|
    JPWO2003029899A1|2005-01-20|
    CN1245665C|2006-03-15|
    EP1431822A1|2004-06-23|
    TWI306881B|2009-03-01|
    CN1556939A|2004-12-22|
    WO2003029899A1|2003-04-10|
    EP1431822A4|2005-01-05|
    KR100905682B1|2009-07-03|
    JP3882817B2|2007-02-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-09-26|Priority to JP2001293269
    2001-09-26|Priority to JPJP-P-2001-00293269
    2002-09-18|Application filed by 닛산 가가쿠 고교 가부시키 가이샤
    2002-09-18|Priority to PCT/JP2002/009559
    2004-05-31|Publication of KR20040044970A
    2009-07-03|Application granted
    2009-07-03|Publication of KR100905682B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP2001293269|2001-09-26|
    JPJP-P-2001-00293269|2001-09-26|
    PCT/JP2002/009559|WO2003029899A1|2001-09-26|2002-09-18|Positive photosensitive polyimide resin composition|
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