JP5136079B2 - Positive photosensitive resin composition for low-temperature curing, method for producing pattern cured film, and electronic component - Google Patents

Description

  The present invention relates to a positive-type photosensitive resin composition for low-temperature curing, a method for producing a patterned cured film, and an electronic component, and more specifically, a heat-resistant positive-type for low-temperature curing containing a heat-resistant polymer having photosensitivity. The present invention relates to a photosensitive resin composition, a method for producing a patterned cured film using the same, and an electronic component.

  Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like has been used for a surface protective film and an interlayer insulating film of a semiconductor element. However, in recent years, with the progress of higher integration and larger size of semiconductor elements, there has been a demand for thinner and smaller sealing resin packages, and LOC (lead-on-chip) and surface mounting methods such as solder reflow have been adopted. Therefore, a polyimide resin excellent in mechanical properties, heat resistance and the like has been required more than ever.

  On the other hand, photosensitive polyimide having a photosensitive property imparted to the polyimide resin itself has been used. However, if this is used, the pattern production process can be simplified and complicated manufacturing processes can be shortened. A heat-resistant photoresist using a conventional photosensitive polyimide or its precursor and its application are well known. In the negative type, a method of introducing a methacryloyl group into a polyimide precursor via an ester bond or an ionic bond (for example, see Patent Documents 1 to 4), a soluble polyimide having a photopolymerizable olefin (for example, see Patent Documents 5 to 10) ), A self-sensitized polyimide having a benzophenone skeleton and an alkyl group at the ortho position of an aromatic ring to which a nitrogen atom is bonded (see, for example, Patent Documents 11 and 12).

  Since the negative photosensitive resin requires an organic solvent such as N-methylpyrrolidone during development, a positive photosensitive resin that can be developed with an alkaline aqueous solution has been recently proposed. In the positive type, a method in which an o-nitrobenzyl group is introduced into a polyimide precursor via an ester bond (for example, see Non-Patent Document 1), a method in which a naphthoquinonediazide compound is mixed in a soluble hydroxylimide or polyoxazole precursor (for example, , Patent Documents 13 and 14), a method of introducing naphthoquinone diazide into soluble polyimide via an ester bond (for example, see Non-Patent Document 2), and a method of mixing naphthoquinone diazide with a polyimide precursor (for example, see Patent Document 15). )and so on.

  However, the above-mentioned negative photosensitive resin has a problem in terms of function and resolution, and depending on the application, there are problems such as a decrease in yield during manufacture. In addition, since the structure of the polymer to be used is limited in the above, the physical properties of the finally obtained film are limited, which is not suitable for multipurpose use. On the other hand, the positive type photosensitive resin also has the same problems because the sensitivity and resolution are low and the structure is limited due to the problem with the absorption wavelength of the photosensitive agent as described above.

  Also, carboxylic acids such as polybenzoxazole precursor mixed with a diazonaphthoquinone compound (see, for example, Patent Document 16), or polyamic acid having a phenol moiety introduced via an ester bond (for example, see Patent Document 17). Instead of these, phenolic hydroxyl groups have been introduced, but these have insufficient developability, resulting in film loss at unexposed areas and peeling of the resin from the substrate. For the purpose of improving developability and adhesion, a mixture of polyamic acids having a siloxane moiety in the polymer skeleton has been proposed (for example, see Patent Documents 18 and 19). Storage stability deteriorates due to use. In addition, for the purpose of improving storage stability and adhesion, those having amine end groups sealed with a polymerizable group (for example, see Patent Documents 20 to 22) have been proposed. Since a diazoquinone compound containing a large number of aromatic rings is used as an agent, there is a problem that the mechanical properties after thermosetting are remarkably lowered due to low sensitivity and the need to increase the amount of diazoquinone compound added. Is.

  In order to improve the problems of the diazoquinone compound, those using various chemical amplification systems have been proposed. Examples of such materials include chemically amplified polyimide (see, for example, Patent Document 23), chemically amplified polyimide, or polybenzoxazole precursor (for example, see Patent Documents 24 to 30). However, in these, in order to achieve high sensitivity, a low molecular weight component is used, and in that case, a decrease in film characteristics caused by the low molecular weight is seen, and conversely, in order to obtain a film having excellent film characteristics. Therefore, a high molecular weight component is used, and a decrease in sensitivity due to insufficient solubility caused by such a high molecular weight is observed, and it is difficult to say that both are materials at a practical level.

  In addition, attempts have been made to obtain a positive photosensitive composition excellent in resolution, sensitivity, and residual film ratio using a polymer having a molecular weight dispersity adjusted, a compound having a phenolic hydroxyl group, and a specific diazoquinone compound (for example, Patent Document 31). Photosensitive polyimide or photosensitive polybenzoxazole is usually cured at a high temperature around 350 ° C. after pattern formation. It is only disclosed that the composition described in Patent Document 31 is also used for such high temperature curing.

  On the other hand, MRAM (Magnet Resistive RAM), which has recently emerged as a promising next-generation memory, is vulnerable to high-temperature processes, and low-temperature processes are desired. Therefore, even a buffer coat (surface protective film) material can be cured at a low temperature of about 280 ° C. or lower, not at a conventional high temperature of around 350 ° C., and the physical properties of the cured film are cured at a high temperature. Buffer coating materials that can provide incomparable performance have become essential. However, there has been a problem that a positive photosensitive resin composition that can be cured at such a low temperature and has performance comparable to that cured at a high temperature has not yet been obtained.

JP-A-49-115541 Japanese Patent Laid-Open No. 51-40922 JP 54-145794 A JP 56-38038 A JP 59-108031 A JP 59-220730 A JP 59-232122 A Japanese Unexamined Patent Publication No. 60-6729 JP-A-60-72925 JP-A-61-57620 JP 59-219330 A JP 59-231533 A JP-A 64-60630 US Pat. No. 4,395,482 JP 52-13315 A Japanese Patent Publication No. 64-46862 JP-A-10-307393 JP-A-4-31861 Japanese Patent Laid-Open No. 4-46345 JP-A-5-197153 JP-A-9-183846 JP 2001-183835 A Japanese Patent Laid-Open No. 3-763 JP 7-219228 A Japanese Patent Laid-Open No. 10-186664 Japanese Patent Laid-Open No. 11-202489 JP 2001-56559 A JP 2001-194791 A JP 2002-526793 A US Pat. No. 6,143,467 JP 2002-122991 A J. et al. Macromol. Sci. Chem. , A24, 12, 1407, 1987 Macromolecules, 23, 4796, 1990

  The present invention has been made to solve the conventional problems as described above, and the problem is excellent curing even at low temperature curing of 280 ° C. or lower, preferably 250 ° C. or lower, more preferably 200 ° C. or lower. The object is to provide a positive photosensitive resin composition having film characteristics. And, by using a polyimide or polybenzoxazole photosensitive resin film having a specific structural unit mainly having a branched structure as a base resin, a performance comparable to that obtained by curing the film at a high temperature can be obtained. The present inventors have found that a positive photosensitive resin composition for low-temperature curing, a method for producing a patterned cured film, and an electronic component can be obtained.

  That is, the positive-type photosensitive resin composition for low-temperature curing according to the present invention is a positive-type photosensitive resin composition for low-temperature curing used for forming a cured film by heat treatment at 280 ° C. or less, and (a) It comprises polybenzoxazole (PBO), polyimide (PI) or a precursor thereof having a branched structure, and (b) a compound that generates an acid by light.

  In the positive photosensitive resin composition according to the present invention, the component (a) is a polyvalent amine having 3 or more amino groups, or a polyvalent acid anhydride having 3 or more anhydride groups. At least selected from the group consisting of polyvalent carboxylic acids or polyvalent carboxylic acid derivatives having three or more functional groups derived from carboxyl groups or carboxyl groups, and polyvalent isocyanates having three or more isocyanate groups It is synthesized using one kind of compound.

  In the positive photosensitive resin composition according to the present invention, the component (a) has a fatty chain.

  In the positive photosensitive resin composition according to the present invention, the component (b) is an o-quinonediazide compound.

  In the positive photosensitive resin composition according to the present invention, the component (c) further includes a compound that can be crosslinked with the component (a) by heat, or that can be polymerized by itself. To do.

  In the positive photosensitive resin composition according to the present invention, the component (c) is a compound having at least one methylol group or alkoxyalkyl group in the molecule.

（式中、Ｘは単結合又は一価〜四価の有機基を示し、Ｒ¹及びＲ²は各々独立に水素原子又は一価の有機基を示し、ａは１〜４の整数であり、ｂ及びｃは各々独立に０〜４の整数である。） In the positive photosensitive resin composition according to the present invention, the component (c) is a compound represented by the following general formula (1).

(In the formula, X represents a single bond or a monovalent to tetravalent organic group, R ¹ and R ² each independently represents a hydrogen atom or a monovalent organic group, a is an integer of 1 to 4, b and c are each independently an integer of 0 to 4.)

（式中、２つのＹは各々独立に水素原子、炭素原子数１〜１０のアルキル基又はその一部に酸素原子若しくはフッ素原子を含む基であり、Ｒ³〜Ｒ⁶は各々独立に水素原子又は一価の有機基を示し、ｄ及びｅは各々独立に１〜３の整数であり、ｆ及びｇは各々独立に０〜４の整数である。） In the positive photosensitive resin composition according to the present invention, the component (c) is a compound represented by the following general formula (2).

(In the formula, two Y's are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a group containing an oxygen atom or a fluorine atom in a part thereof, and R ^{3 to} R ⁶ are each independently a hydrogen atom. Or a monovalent organic group, d and e are each independently an integer of 1 to 3, and f and g are each independently an integer of 0 to 4).

（式中、複数のＲ⁷及びＲ⁸は各々独立に水素原子又は一価の有機基を示し、Ｒ^8'は二価の有機基である。） In the positive photosensitive resin composition according to the present invention, the component (c) is a compound represented by the following general formula (3).

(In the formula, each of R ⁷ and R ⁸ independently represents a hydrogen atom or a monovalent organic group, and R ^{8 ′} represents a divalent organic group.)

  Further, in the method for producing a patterned cured film according to the present invention, the photosensitive resin film formation is performed in which the positive photosensitive resin composition for low temperature curing is applied on a support substrate and dried to form a photosensitive resin film. A step of exposing the photosensitive resin film to a predetermined pattern, a developing step of developing the exposed photosensitive resin film using an alkaline aqueous solution to obtain a patterned resin film, and the pattern after development And a heat treatment step of heat-treating the resin film at a temperature of 280 ° C. or lower to obtain a pattern cured film.

  In the method for producing a cured pattern film according to the present invention, the heat treatment temperature is 200 ° C. or lower in the step of heat-treating the patterned resin film after development.

  In the electronic component according to the present invention, the pattern cured film obtained by the method for producing a pattern cured film is at least one selected from the group consisting of an interlayer insulating film layer, a rewiring layer, and a surface protective film layer. It is characterized by having as.

  In the electronic component according to the present invention, the electronic component is a magnetoresistive memory.

  Conventional dehydration ring closure requires curing at a high temperature of about 350 ° C., but by using the positive photosensitive resin composition of the present invention as a base resin, the cured film can be cured even at a low temperature of 200 ° C. or less. Performance comparable to that cured at high temperature is obtained. Moreover, according to the method for producing a patterned cured film of the present invention, a cured pattern film having a good shape and excellent sensitivity, resolution and cured film characteristics can be obtained by using the positive photosensitive resin composition. Furthermore, since it can be cured by a low temperature process, damage to the device can be avoided and a highly reliable electronic component can be obtained.

  Hereinafter, embodiments of a positive photosensitive resin composition for low-temperature curing, a method for producing a patterned cured film, and an electronic component according to the present invention will be described in detail. In addition, this invention is not limited by this embodiment.

[Positive photosensitive resin composition for low-temperature curing]
The positive-type photosensitive resin composition for low-temperature curing according to the present invention comprises (a) polybenzoxazole (PBO), polyimide (PI) or a precursor thereof (hereinafter referred to as (a) component) having a branched structure. And (b) a compound that generates an acid by light (hereinafter referred to as component (b)).

[(A) component]
The component (a) in the low-temperature curing positive photosensitive resin composition according to the present invention is polybenzoxazole (PBO), polyimide (PI) or a precursor thereof having a branched structure. The term “branched structure” as used herein refers to, for example, those in which the repeating unit serving as the basis of the polymer has various forms in which the repeating unit is not linear but branched, or is different in constituent monomer from the repeating unit of the main chain. It can be broadly divided into those with side chains attached. The former includes a group of polymers called hyperbranched polymers such as dendrimers. In the polymer used in the present invention, the main repeating unit structure is polybenzoxazole (PBO), polyimide (PI) or a precursor thereof, and the branched structure may be in any one of the above forms, It is not limited.

  As these synthesis methods, for example, a trifunctional or higher polyfunctional monomer is used as a constituent component when synthesizing the polymer, so that the repeating unit is not linear but is branched in some places. It is done. As a method for synthesizing a branched polymer classified as a hyperbranched polymer, for example, a method disclosed in non-patent literature: M. Kakimoto et. Al., Polym. J., 35, 586 (2003). Can be mentioned.

  For the main chain repeating unit mentioned as the latter, the side chain with a different constituent monomer is bonded, and the polymer chain that does not necessarily match the main chain repeating unit is graft polymerized based on the main chain functional group. And the like. For example, examples of the functional group of the main chain serving as a base point include a phenol group of a PBO precursor and a carboxyl group of a PI precursor. The synthesis method mentioned here is an example and does not limit the branched polymer of the present invention. Among them, a method using a polyfunctional monomer can be mentioned as a simple and preferable synthesis method and polymer purification.

Next, PBO, PI and their precursors mainly constituting the branched polymer will be described.
For example, a polyamide which is a PBO precursor can be obtained, for example, by reacting dicarboxylic acid dichloride with a diamine. The polyamic acid used as the PI precursor can be obtained, for example, by reacting tetracarboxylic dianhydride with diamine. The polyamic acid ester can be obtained, for example, by reacting a tetracarboxylic acid diester dichloride with a diamine. PBO and PI can be further obtained by dehydrating and ring-closing them.

  In particular, for electronic components, polyhydroxyamides that can be closed to polybenzoxazole by heating are now being used widely as being excellent in heat resistance, mechanical properties, and electrical properties. This polyhydroxyamide has a repeating unit represented by the following general formula (4). The amide unit containing a hydroxy group is finally converted into an oxazole having excellent heat resistance, mechanical properties, and electrical properties by dehydration and ring closure at the time of curing.

（式中、Ｕは四価の有機基を示し、Ｖは二価の有機基を示す。）

(In the formula, U represents a tetravalent organic group, and V represents a divalent organic group.)

In the branched polymer that can be used in the present invention, examples of the main repeating unit include a repeating unit represented by the following general formula (5). This polyhydroxyamide only needs to have the above repeating unit. However, since the solubility of the polyhydroxyamide in an alkaline aqueous solution is derived from a phenolic hydroxyl group, an amide unit containing a hydroxy group is contained in a certain proportion or more. It is preferable.
That is, the following general formula (5)

（式中、Ｕは四価の有機基を示し、ＶとＷは二価の有機基を示す。ｈとｉは、モル分率を示し、ｈとｉの和は１００モル％であり、ｈが６０〜１００モル％、ｉが４０〜０モル％である。）で表されるポリヒドロキシアミドであることが好ましい。ここで、式中のｈとｉのモル分率は、ｈ＝８０〜１００モル％、ｉ＝２０〜０モル％であることがより好ましい。

(In the formula, U represents a tetravalent organic group, V and W represent a divalent organic group, h and i represent a mole fraction, and the sum of h and i is 100 mol%, h Is 60 to 100 mol%, and i is 40 to 0 mol%.). Here, the molar fraction of h and i in the formula is more preferably h = 80 to 100 mol% and i = 20 to 0 mol%.

  In the present invention, the repeating unit represented by the general formula (5) can generally be synthesized from a dicarboxylic acid derivative and a hydroxy group-containing diamine. Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting with the diamines. As the dihalide derivative, a dichloride derivative is preferable.

  The dichloride derivative can be synthesized by reacting a dicarboxylic acid derivative with a halogenating agent. As the halogenating agent, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride, etc., which are used in the usual acid chlorideation reaction of carboxylic acid can be used.

  As a method of synthesizing the dichloride derivative, it can be synthesized by reacting the dicarboxylic acid derivative and the halogenating agent in a solvent, or reacting in an excess halogenating agent and then distilling off the excess. As the reaction solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, benzene and the like can be used.

  The amount of these halogenating agents to be used in a solvent is preferably 1.5 to 3.0 mol, more preferably 1.7 to 2.5 mol relative to the dicarboxylic acid derivative. When making it react in an agent, 4.0-50 mol is preferable and 5.0-20 mol is more preferable. The reaction temperature is preferably -10 to 70 ° C, more preferably 0 to 20 ° C.

  The reaction between the dichloride derivative and the diamine is preferably performed in an organic solvent in the presence of a dehydrohalogenating agent. As the dehydrohalogenating agent, organic bases such as pyridine and triethylamine are usually used. As the organic solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide and the like can be used. The reaction temperature is preferably −10 to 30 ° C., more preferably 0 to 20 ° C.

  Here, in the above general formulas (4) and (5), the tetravalent organic group represented by U generally means that two hydroxy groups that react with a dicarboxylic acid to form a polyamide structure are amines. Is a residue of a diamine having a structure located in the ortho position of the tetravalent aromatic group, preferably a tetravalent aromatic group, preferably having 6 to 40 carbon atoms, and a tetravalent aromatic group having 6 to 40 carbon atoms. Groups are more preferred. As the tetravalent aromatic group, those in which all four bonding sites are present on the aromatic ring are preferable.

  Such diamines include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane. Bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3-amino-) 4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3- Although hexafluoropropane etc. are mentioned, it is not limited to these. These compounds can be used alone or in combination of two or more.

  In the formula of the polyamide, the divalent organic group represented by W is generally a residue of a diamine that reacts with a dicarboxylic acid to form a polyamide structure, and other than the diamine that forms the U. It is a residue and is preferably a divalent aromatic group or an aliphatic group. The number of carbon atoms is preferably 4 to 40, and more preferably a divalent aromatic group having 4 to 40 carbon atoms.

Examples of such diamines include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p. -Phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4 Examples of aromatic diamine compounds such as-(4-aminophenoxy) phenyl] ether and 1,4-bis (4-aminophenoxy) benzene, and other diamines containing a silicone group include LP-7100, X-22 161AS, X-22-161A, X-22-16 1B, X-22-161C, and X-22-161E (all are trade names manufactured by Shin-Etsu Chemical Co., Ltd.) and the like, but are not limited thereto.
These compounds can be used alone or in combination of two or more.

  In the above general formulas (4) and (5), the divalent organic group represented by V is a dicarboxylic acid residue that reacts with diamine to form a polyamide structure, and has a heat resistant viewpoint. And a divalent aromatic group is preferred, and the number of carbon atoms is preferably 6 to 40, more preferably a divalent aromatic group having 6 to 40 carbon atoms. As the divalent aromatic group, one in which two bonding sites are both present on the aromatic ring is preferable.

  On the other hand, a group containing an aliphatic chain structure having 1 to 30 carbon atoms or an alicyclic structure having 4 to 30 carbon atoms from the viewpoint that high mechanical strength can be obtained even at a low temperature of 200 ° C. or lower. It is preferable that it is group containing.

  Examples of such dicarboxylic acids include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane, and 4,4′-dicarboxybiphenyl. 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid Aromatic dicarboxylic acids such as 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, oxalic acid, malonic acid, dimethylmalonic acid, ethyl Ronic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid Glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, Octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluoro Sebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, Ntadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosandioic acid, heneicosandioic acid, docosandioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosan diacid Acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid

（式中、Ｚは炭素原子数１〜６の炭化水素基、ｊは１〜６の整数である。）等が挙げられるがこれらに限定されるものではない。
これらの化合物を、単独で又は２種以上を組み合わせて使用することができる。

(Wherein, Z is a hydrocarbon group having 1 to 6 carbon atoms, and j is an integer of 1 to 6), etc., but is not limited thereto.
These compounds can be used alone or in combination of two or more.

  Next, a preferred polyamic acid or polyamic acid ester as the main repeating unit of the branched polymer in the present invention will be described. As a preferred structure, one represented by the following general formula (7) can be exemplified.

(式中、Ｒ⁹は少なくとも２個以上の炭素原子を有する二価から八価の有機基、Ｒ¹⁰は少なくとも２個以上の炭素原子を有する二価から六価の有機基、Ｒ¹¹は水素又は炭素原子数１から２０までの有機基を示す。ｌは２から１００,０００までの整数、ｋは０から２までの整数、ｍ、ｎは０から４までの整数を示す。また、ｍ+ｎ＞０である。）

(Wherein R ⁹ is a divalent to octavalent organic group having at least 2 carbon atoms, R ¹⁰ is a divalent to hexavalent organic group having at least 2 carbon atoms, and R ¹¹ is hydrogen. Or an organic group having 1 to 20 carbon atoms, l is an integer from 2 to 100,000, k is an integer from 0 to 2, m, and n is an integer from 0 to 4. + n> 0.)

R ⁹ in the general formula (7) represents a structural component of an acid dianhydride, and the acid dianhydride contains an aromatic ring and has at least two carbon atoms. It is preferably a valent organic group, and more preferably a trivalent or tetravalent organic group having 6 to 30 carbon atoms.

Specifically, it is preferable that the R ⁹ (COOR ¹¹ ) _k (OH) _m group in the general formula (7) has a structure as shown in the following general formula (8).

In this case, R ¹² and R ¹⁴ in the general formula (8) each represent a divalent to tetravalent organic group selected from 2 to 20 carbon atoms, but are more aromatic than the heat resistance of the resulting polymer. Those containing a ring are preferred, and among them, particularly preferred structures include trimellitic acid, trimesic acid, naphthalene tricarboxylic acid residues and the like.

R ¹³ in the general formula (8) is preferably a trivalent to hexavalent organic group selected from 3 to 20 carbon atoms. Further, the p number of hydroxyl groups bonded to R ¹³ are preferably located adjacent to the amide bond. Examples of such R ¹³ (OH) _p groups include fluorine atoms containing bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-hydroxy-4-aminophenyl) hexafluoropropane, No fluorine atom, bis (3-amino-4-hydroxyphenyl) propane, bis (3-hydroxy-4-aminophenyl) propane, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3 Mention of amino group of '-diamino-4,4'-dihydroxybiphenyl, 2,4-diamino-phenol, 2,5-diaminophenol, 1,4-diamino-2,5-dihydroxybenzene, etc. Can do.

In addition, R ¹⁵ and R ¹⁶ in the general formula (8) are each preferably hydrogen or an organic group having 1 to 20 carbon atoms. When the number of carbon atoms is greater than 20, the solubility in an alkaline developer is lowered.

  Moreover, o and q in the said General formula (8) represent the integer of 0-2, p represents the integer of 1-4. When p is 5 or more, the properties of the resulting heat-resistant resin film deteriorate.

Among the compounds represented by the general formula (8), the R ⁹ (COOR ¹¹ ) _k (OH) _m group in the general formula (7) is a preferable R ⁹ (COOR ¹¹ ) _k (OH) _m group. Illustrative examples include those having the structure shown in chemical formula (9) below, but are not limited thereto.

  Moreover, it can also modify | denature with the tetracarboxylic acid and dicarboxylic acid which do not have a hydroxyl group in the range which does not impair the solubility with respect to an alkali, photosensitive performance, and heat resistance. Examples of this include aromatic tetracarboxylic acids such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, and diphenylsulfone tetracarboxylic acid, and two carboxyl groups thereof as methyl or ethyl groups. Diester compounds, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid, diester compounds in which two carboxyl groups are methyl or ethyl groups, terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalene dicarboxylic acid Examples thereof include aromatic dicarboxylic acids such as acids, and aliphatic dicarboxylic acids such as adipic acid.

  These are preferably modified by 50 mol% or less of the acid component, more preferably 30 mol% or less. If the modification exceeds 50 mol%, the alkali solubility and photosensitivity may be impaired.

R ¹⁰ in the general formula (7) represents a structural component of diamine. Among these, as R ¹⁰ , those having aromaticity are preferred from the heat resistance of the obtained polymer. Specific examples of the R ¹⁰ (OH) _n group include a bis (amino-hydroxy-phenyl) hexafluoropropane having a fluorine atom, a diaminodihydroxypyrimidine having no fluorine atom, a diaminodihydroxypyridine, a hydroxy- Examples thereof include compounds such as diamino-pyrimidine, diaminophenol, dihydroxybenzidine, and structures having the following general formulas (10), (11), and (12).

Among these, R ¹⁷ and R ^{19 in} the general formula (10), R ^{21 in} the general formula (11), and R ²⁴ in the general formula (12) are aromatic rings based on the heat resistance of the obtained polymer. An organic group having is preferred. R ¹⁸ in the general formula (10), R ²⁰ and R ^{22 in} the general formula (11), and R ²³ in the general formula (12) are organic groups having an aromatic ring from the heat resistance of the obtained polymer. preferable. Moreover, r and s of General formula (10) show the integer of 1 or 2, t of General formula (11) and u of General formula (12) show the integer of 1-4.

Furthermore, among the R ¹⁰ (OH) _n groups in the general formula (7), a specific example represented by the general formula (10) is shown in the following chemical formula (13).

Further, among the R ¹⁰ (OH) _n groups in the general formula (7), a specific example represented by the general formula (11) is shown in the following chemical formula (14).

Further, among the R ¹⁰ (OH) _n groups in the general formula (7), a specific example represented by the general formula (12) is shown in the following chemical formula (15).

In the general formula (10), R ¹⁷ and R ¹⁹ are each a trivalent to tetravalent organic group selected from 2 to 20 carbon atoms. R ¹⁷ (OH) _r group and R ¹⁹ (OH) _s group are specifically hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis (hydroxyphenyl) It represents a hexafluoropropane group, a bis (hydroxyphenyl) propane group, a bis (hydroxyphenyl) sulfone group, a hydroxydiphenyl ether group, a dihydroxydiphenyl ether group, and the like. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used.

R ¹⁸ in the general formula (10) represents a divalent organic group having 2 to 30 carbon atoms. A divalent group having aromaticity is preferable from the heat resistance of the obtained polymer, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. In addition, an aliphatic cyclohexyl group can also be used.

In the general formula (11), R ²⁰ and R ²² each represent a divalent organic group having 2 to 20 carbon atoms. A divalent group having aromaticity is preferable from the heat resistance of the obtained polymer, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. In addition, an aliphatic cyclohexyl group or the like can also be used. R ²¹ represents a trivalent to hexavalent organic group selected from 3 to 20 carbon atoms, and preferably has an aromatic ring from the heat resistance of the resulting polymer. Specifically, the R ²¹ (OH) _t group is a hydroxyphenyl group, a dihydroxyphenyl group, a hydroxynaphthyl group, a dihydroxynaphthyl group, a hydroxybiphenyl group, a dihydroxybiphenyl group, a bis (hydroxyphenyl) hexafluoropropane group, a bis (Hydroxyphenyl) propane group, bis (hydroxyphenyl) sulfone group, hydroxydiphenyl ether group, dihydroxydiphenyl ether group and the like are represented. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used.

In the above general formula (12), R ²³ represents a divalent organic group selected from 2 to 20 carbon atoms. Due to the heat resistance of the polymer obtained, an aromatic divalent group is preferable, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. In addition, an aliphatic cyclohexyl group or the like can also be used. R ²⁴ represents a trivalent to hexavalent organic group selected from 3 to 20 carbon atoms, and preferably has an aromatic ring from the heat resistance of the resulting polymer. Specifically, the R ²⁴ (OH) _u group is a hydroxyphenyl group, a dihydroxyphenyl group, a hydroxynaphthyl group, a dihydroxynaphthyl group, a hydroxybiphenyl group, a dihydroxybiphenyl group, a bis (hydroxyphenyl) hexafluoropropane group, a bis ( Hydroxyphenyl) propane group, bis (hydroxyphenyl) sulfone group, hydroxydiphenyl ether group, dihydroxydiphenyl ether group and the like are represented. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used.

  It can also be modified using other diamine components. Examples include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone or their fragrances. Examples thereof include aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and the like, such as compounds in which an aromatic ring is substituted with an alkyl group or a halogen atom. When using these, the range of 1-40 mol% is preferable. When such a diamine component is copolymerized in excess of 40 mol%, the heat resistance of the resulting polymer tends to decrease.

R ^{11 in the} general formula (7) represents hydrogen or an organic group having 1 to 20 carbon atoms. From the viewpoint of the stability of the resulting positive photosensitive resin precursor solution, R ¹¹ is preferably an organic group, but hydrogen is preferred from the viewpoint of the solubility in an aqueous alkali solution. In the present invention, a hydrogen atom and an alkyl group can be mixed. By controlling the amount of hydrogen and organic group of R ^11, the dissolution rate with respect to the aqueous alkali solution is changed, so that a positive photosensitive resin precursor composition having an appropriate dissolution rate can be obtained by this adjustment. . A preferred range is that 10% to 90% of R ¹¹ is a hydrogen atom. If the number of carbon atoms in R ¹¹ exceeds 20, it will not dissolve in the alkaline aqueous solution. From the above, R ¹¹ preferably contains at least one hydrocarbon group having 1 to 16 carbon atoms, and the others are hydrogen atoms.

  Next, the polyfunctional monomer used for introducing the branched structure will be described. In this method using a polyfunctional monomer, the polyfunctional monomer that can be used in the synthesis of the branched polymer of the present invention is not limited as long as it can introduce a branch point into the polymer chain. Among such monomers, polyvalent amines having 3 or more amino groups, polyhydric acid anhydrides having 3 or more anhydride groups, carboxyl groups or three functional groups derived from carboxyl groups The polyvalent carboxylic acids or polyvalent carboxylic acid derivatives having the above, and polyvalent isocyanates having three or more isocyanate groups can be preferably used from the viewpoint of ease of synthesis and high reactivity.

  The introduction ratio of the polyfunctional monomer added during the synthesis of the component (a) in the present invention is as follows with respect to the diamine component in the case of polyvalent isocyanates, polyvalent amines, polyvalent carboxylic acids and derivatives thereof, and polyhydric acid anhydrides. In the range of 0.1 to 70 mol%, and preferably 0.5 to 65 mol%, a polymer having the above degree of dispersion can be easily obtained. When the introduction ratio is less than 0.1 mol%, the degree of dispersion tends to be 2.1 or less, and when a positive photosensitive resin precursor composition is produced using this polymer, it has high resolution but low sensitivity. Therefore, it does not have the high resolution and high sensitivity of the present invention. Further, when the introduction ratio exceeds 70 mol%, when a positive photosensitive resin composition is produced using this polymer, it tends to have high sensitivity but low resolution. There is a risk of not satisfying the sensitivity.

  The method for adding these compounds will be described using polyvalent amines as an example. As one method, in order to form the structural unit represented by the general formula (7), it can be added together with a diamine. In addition, after the dicarboxylic acid halide and the polyvalent amine are previously reacted to form the structural unit represented by the general formula (7), the structural unit represented by the general formula (7) is added to the system. A method of adding a diamine to form, or conversely, a structural unit represented by the general formula (7) is formed using an excess of dicarboxylic acid halide, and then a polyvalent amine is added to connect segments. It is also possible to add them sequentially.

  The polyvalent amines referred to here are compounds having 3 or more amino groups, and specific examples include compounds represented by the following chemical formula (16).

  The polyhydric acid anhydrides referred to here are compounds having three or more anhydride groups, and specific examples thereof include compounds represented by the following general formula (17).

（式中、Ｒ²⁶は、酸素原子又は窒素原子を表す。） In the general formula (17), R ²⁵ is a group represented by the following general formula (18).

(In the formula, R ²⁶ represents an oxygen atom or a nitrogen atom.)

  The polyvalent carboxylic acids and derivatives are compounds having three or more carboxyl groups or functional groups derived from carboxylic acids. Derivatives of polyvalent carboxylic acids include, but are not limited to, acid halides, esters, amides and the like. From the viewpoint of reactivity, acid halides are preferable, and acid chlorides are particularly preferable.

  Specifically, a compound represented by the following general formula (19) can be exemplified.

（式中、Ｌは各々独立に水素原子又は塩素原子を表す。）

(In the formula, each L independently represents a hydrogen atom or a chlorine atom.)

  Polyvalent isocyanates are compounds having three or more isocyanate groups, and specific examples include compounds represented by the following chemical formula (20).

  Preferable examples of the polyfunctional monomer are 2,4,6-triaminopyridine, 2,4,6-triaminopyrimidine, tricarboxylic acid chloride, and 3,4,4'-triaminodiphenyl ether.

These compounds introduced into the polymer at the time of synthesis can be easily detected by the following method. For example, this polymer is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component, which are constituent units of the polymer, and this is analyzed by gas chromatography (GC) or NMR measurement to obtain the compound used in the present invention. It can be easily detected. Apart from this, the polymer component can be easily detected directly by pyrolysis gas chromatograph (PGC), infrared spectrum and C ¹³ NMR spectrum measurement.

  The molecular weight of the component (a) is preferably 3,000 to 200,000, more preferably 5,000 to 100,000 in terms of weight average molecular weight. Here, the weight average molecular weight is a value obtained by measuring by a gel permeation chromatography method and converting from a standard polystyrene calibration curve. Moreover, the preferable dispersion degree of (a) component is 2.2 or more, Preferably it is 2.2 to 10. This can also be realized by mixing polymers included in the category of two or more components (a) having different molecular weights.

[Component (c)]
Next, since the relationship with the component (a) is close, the component (c) will be described prior to the component (b).
The positive-type photosensitive resin composition for low-temperature curing according to the present invention preferably contains, as the component (c), a compound that can be cross-linked with the component (a) by heat or polymerized by itself. This component (c) reacts and crosslinks with the polybenzoxazole precursor or polybenzoxazole in the step of heat treatment after coating, exposure and development. Alternatively, the compound itself is polymerized in the heat treatment step. Thereby, the brittleness of the film, which is a concern at curing at a relatively low temperature, for example, 200 ° C. or less, can be prevented, and the mechanical properties can be improved.

  The temperature at which the component (c) can be crosslinked is preferably 150 ° C. or higher so that crosslinking does not proceed in the coating, drying, exposure, and development steps of the photosensitive resin composition.

  The component (c) is not particularly limited except that it is a compound that crosslinks or polymerizes in the heat treatment step, but is preferably a compound having a methylol group, an alkoxymethyl group, an epoxy group, or a vinyl ether group in the molecule. A compound in which these groups are bonded to a benzene ring, or a melamine resin or urea resin in which the N-position is substituted with a methylol group and / or an alkoxymethyl group is preferable. In addition, a compound in which these groups are bonded to a benzene ring having a phenolic hydroxyl group is more preferable in that the sensitivity can be improved by increasing the dissolution rate of the exposed area during development. Among them, a compound having two or more methylol groups and alkoxymethyl groups in the molecule is more preferable in that the film can be prevented from melting when the film is cured after the pattern is formed, and the stability of the varnish.

  Although the component (c) is crosslinked with the component (a), it may be a compound that polymerizes between molecules together with the component (a). Among them, the compounds represented by the following general formula (1) are more preferable because they have a small drop in film properties even when cured at a low temperature of 200 ° C. or less and are excellent in film properties.

（式中、Ｘは単結合又は一価〜四価の有機基を示し、Ｒ¹及びＲ²は各々独立に水素原子又は一価の有機基を示し、ａは１〜４の整数であり、ｂ及びｃは各々独立に０〜４の整数である。）

(In the formula, X represents a single bond or a monovalent to tetravalent organic group, R ¹ and R ² each independently represents a hydrogen atom or a monovalent organic group, a is an integer of 1 to 4, b and c are each independently an integer of 0 to 4.)

  In the general formula (1), the organic group represented by X is an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group or a propylene group, or an alkyl group having 2 to 10 carbon atoms such as an ethylidene group. Arylene groups having 6 to 30 carbon atoms such as alkylidene groups and phenylene groups, groups in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine atoms, sulfone groups, carbonyl groups, ether bonds , A thioether bond, an amide bond, and the like, and a divalent organic group represented by the following general formula (21) is preferable.

（式中、個々のＭは、各々独立にアルキレン基（例えば炭素原子数が１〜１０のもの）、アルキリデン基（例えば炭素原子数が２〜１０のもの）、それらの水素原子の一部又は全部をハロゲン原子で置換した基、スルホン基、カルボニル基、エーテル結合、チオエーテル結合、アミド結合等から選択されるものである。また、Ｒ²⁷は水素原子、ヒドロキシ基、アルキル基又はハロアルキル基であり、複数存在する場合は互いに同一でも異なっていてもよく、ｖは１〜１０の整数である。）

(In the formula, each M is independently an alkylene group (for example, having 1 to 10 carbon atoms), an alkylidene group (for example, having 2 to 10 carbon atoms), a part of those hydrogen atoms or A group in which all are substituted with a halogen atom, a sulfone group, a carbonyl group, an ether bond, a thioether bond, an amide bond, etc. R ²⁷ is a hydrogen atom, a hydroxy group, an alkyl group or a haloalkyl group. In the case where a plurality of units are present, they may be the same or different, and v is an integer of 1 to 10.)

In the above general formula (1), the monovalent organic groups of R ¹ and R ² are specifically methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl. A hydrocarbon group such as a group or an amyl group is exemplified as a typical example, but is not limited thereto.

  Further, as the component (c), those listed in the following general formula (2) are photosensitive characteristics, and those listed in the following general formula (3) are solvent resistance of a cured film in curing at a low temperature of 200 ° C. or lower, Since it is excellent also in flux tolerance, it is mentioned as a particularly preferable thing.

（式中、２つのＹは各々独立に水素原子、炭素原子数１〜１０のアルキル基又はその一部に酸素原子若しくはフッ素原子を含んでいる基、Ｒ^３〜Ｒ⁶は各々独立に水素原子又は一価の有機基を示し、ｄ及びｅは各々独立に１〜３の整数であり、ｆ及びｇは各々独立に０〜４の整数である。）

(In the formula, two Y's are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a group containing an oxygen atom or a fluorine atom in a part thereof, and R ^{3 to} R ⁶ are each independently a hydrogen atom. Or a monovalent organic group, d and e are each independently an integer of 1 to 3, and f and g are each independently an integer of 0 to 4).

In the general formula (2), specifically, as Y containing an oxygen atom, there is an alkyloxy group and the like, and as containing a fluorine atom, there is a perfluoroalkyl group. Specific examples of the monovalent organic group represented by R ^{3 to} R ⁶ include hydrocarbons such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, and an amyl group. Groups are illustrated as typical examples, but are not limited thereto.

（式中、複数のＲ⁷及びＲ⁸は各々独立に水素原子又は一価の有機基を示し、Ｒ^8'は二価の有機基である。）

(In the formula, each of R ⁷ and R ⁸ independently represents a hydrogen atom or a monovalent organic group, and R ^{8 ′} represents a divalent organic group.)

  What is represented by the said General formula (3) can mention as a compound shown to the following general formula (22) as a preferable thing.

（式中、Ｑは各々独立に炭素原子数１〜１０の一価のアルキル基を表し、Ｒは各々独立に炭素原子数１〜２０の一価のアルキル基を表す。）

(In the formula, each Q independently represents a monovalent alkyl group having 1 to 10 carbon atoms, and each R independently represents a monovalent alkyl group having 1 to 20 carbon atoms.)

  The content of the component (c) used in the present invention is 0.1 to 50 with respect to 100 parts by weight of the component (a) in order to suppress the sensitivity and resolution at the time of light exposure and the melting of the pattern at the time of curing. It is preferable to set it as a weight part, It is more preferable to set it as 0.1-20 weight part, It is further more preferable to set it as 0.5-20 weight part.

  In order to promote the crosslinking reaction of component (c), an acid catalyst or a compound that generates an acid by heat may be used in combination. The acid used as the catalyst is preferably a strong acid. Specifically, arylsulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid, perfluorosulfonic acid such as camphorsulfonic acid, trifluoromethanesulfonic acid, and nonafluorobutanesulfonic acid. Alkyl sulfonic acids such as alkyl sulfonic acids, methane sulfonic acids, ethane sulfonic acids, butane sulfonic acids are desirable.

  The compound that generates the acid by heat is added as an onium salt to the positive photosensitive resin composition of the present invention in the form of a salt or a covalent bond such as imide sulfonate. Among them, those having a thermal decomposition starting temperature of 50 ° C. to 270 ° C. are desirable. Specifically, it is desirable that the 1% weight loss temperature measured by thermogravimetric analysis (TG) is 50 ° C. to 270 ° C., or the 5% weight loss temperature is 60 ° C. to 300 ° C. Furthermore, those having a thermal decomposition starting temperature of 140 ° C. to 250 ° C. are more preferable because no acid is generated during pre-baking and there is no possibility of adversely affecting the photosensitive characteristics and the like.

  Specifically, it is desirable that the 1% weight loss temperature measured by thermogravimetric analysis (TG) is 140 ° C to 250 ° C, or the 5% weight loss temperature is 170 ° C to 265 ° C. When these acid catalysts or compounds that generate an acid by heat are used, the amount is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, relative to 100 parts by weight of component (a). If the amount added is large, the influence of thermal decomposition during pre-baking may not be negligible.

[Component (b)]
In the positive photosensitive resin composition according to the present invention, the compound (b) that generates an acid by light is used. This component (b) is a photosensitizer and has a function of generating an acid and increasing the solubility of the light irradiated portion in an alkaline aqueous solution. However, it is preferable that the functional groups of the component (a) and the component (c) do not cause bonding (crosslinking) due to the generated acid. Examples of the type include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts and the like. Although there is no particular limitation, the sensitivity of the o-quinonediazide compound is high, and the components (a) and (c) Since the functional group of the component does not cause bonding (crosslinking), it is preferable.

  The o-quinonediazide compound can be obtained, for example, by subjecting o-quinonediazidesulfonyl chlorides to a hydroxy compound, an amino compound or the like in the presence of a dehydrochlorinating agent. Examples of the o-quinonediazide sulfonyl chlorides include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-4-sulfonyl chloride. Etc. can be used.

  Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, and 2,3,4-trihydroxybenzophenone. 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4, 3 ′, 4 ′, 5′-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro -1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2, -a] indene, tris (4-hydroxyphenyl) methane, and tris (4-hydroxyphenyl) ethane can be used.

  Examples of the amino compound include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl. Sulfide, o-aminophenol, m-aminophenol, p-aminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3 -Amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-Amino-4-hydroxyphenyl) hexaph Oropuropan, and bis (4-amino-3-hydroxyphenyl) hexafluoropropane can be used.

  The o-quinonediazide sulfonyl chloride and the hydroxy compound and / or amino compound may be blended so that the total of hydroxy group and amino group is 0.5 to 1 equivalent with respect to 1 mol of o-quinonediazide sulfonyl chloride. preferable. A preferred blending ratio of the dehydrochlorinating agent and o-quinonediazide sulfonyl chloride is in the range of 0.95 / 1 to 1 / 0.95. A preferable reaction temperature is 0 to 40 ° C., and a preferable reaction time is 1 to 10 hours.

  As the reaction solvent, solvents such as dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone and the like are used. Examples of the dehydrochlorinating agent include sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like.

[Other additive components]
In the positive photosensitive resin composition according to the present invention, in addition to the components (a) to (c), (1) a dissolution inhibitor, (2) an adhesion-imparting agent, (3) a surfactant or a leveling agent, etc. These ingredients may be blended.

((1) dissolution inhibitor)
In order to adjust the solubility in an aqueous alkali solution, a dissolution inhibitor that is a compound that inhibits the solubility can be added to the positive photosensitive resin composition according to the present invention. Of these, onium salts, diaryl compounds and tetraalkylammonium salts are preferred. Examples of the onium salt include iodonium salts such as diaryliodonium salts, sulfonium salts such as triarylsulfonium salts, diazonium salts such as phosphonium salts, aryldiazonium salts, and the like.

  Examples of the diaryl compound include those in which two aryl groups such as diarylurea, diarylsulfone, diarylketone, diarylether, diarylpropane, and diarylhexafluoropropane are bonded via a bonding group. A phenyl group is preferred. Examples of the tetraalkylammonium salt include tetraalkylammonium halides in which the alkyl group is a methyl group or an ethyl group.

  Among these, those showing a good dissolution inhibiting effect include diaryl iodonium salts, diaryl urea compounds, diaryl sulfone compounds, tetramethyl ammonium halide compounds, etc., and diaryl urea compounds include diphenyl urea, dimethyl diphenyl urea and the like. Examples of the tetramethylammonium halide compound include tetramethylammonium chloride, tetramethylammonium bromide, and tetramethylammonium iodide.

  Especially, the diaryl iodonium salt compound represented by the following general formula (23) is preferable.

（式中、Ｘ⁻は対陰イオンを示し、Ｒ²⁸及びＲ²⁹は各々独立に一価の有機基を示し、ｗ及びｘは各々独立に０〜５の整数である。）

(In the formula, X ⁻ represents a counter anion, R ²⁸ and R ²⁹ each independently represent a monovalent organic group, and w and x are each independently an integer of 0 to 5).

  The counter anion in the general formula (23) includes nitrate ion, boron tetrafluoride ion, perchlorate ion, trifluoromethanesulfonate ion, p-toluenesulfonate ion, thiocyanate ion, chlorine ion, bromine ion, An iodine ion etc. are mentioned.

  Examples of the diaryliodonium salt include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, and diphenyliodonium. Bromide, diphenyliodonium chloride, diphenyliodonium iodide and the like can be used.

  Among these, diphenyliodonium nitrate, diphenyliodonium trifluoromethanesulfonate, and diphenyliodonium-8-anilinonanaphthalene-1-sulfonate are preferable because of their high effects.

  The blending amount of the dissolution inhibitor is preferably 0.01 to 15 parts by weight, more preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of component (a), from the viewpoints of sensitivity and allowable width of development time. Preferably, 0.05 to 8 parts by weight is more preferable.

((2) Adhesion imparting agent)
The positive photosensitive resin composition of the present invention can contain an adhesion-imparting agent such as an organic silane compound or an aluminum chelate compound in order to improve the adhesion of the cured film to the substrate. Examples of the organic silane compound include vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, urea propyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, n- Propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol Ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene, 1,4-bis ( Ethyldihydroxysilyl) benzene, 1,4-bis (propyldihydroxysilyl) benzene, 1,4-bis (butyldihi Loxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropylhydroxysilyl) benzene, 1,4-bis (dibutylhydroxysilyl) ) Benzene and the like. Examples of the aluminum chelate compound include tris (acetylacetonate) aluminum, acetylacetate aluminum diisopropylate, and the like.

  When using these adhesion grant agents, 0.1-20 weight part is preferable with respect to 100 weight part of (a) component, and 0.5-10 weight part is more preferable.

((3) Surfactant or leveling agent)
In addition, the positive photosensitive resin composition of the present invention may be added with an appropriate surfactant or leveling agent in order to prevent coating properties such as striation (film thickness unevenness) or improve developability. Can do. Examples of such a surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like. Megafax F171 is a commercially available product. F173, R-08 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Florard FC430, FC431 (trade name, manufactured by Sumitomo 3M), organosiloxane polymers KP341, KBM303, KBM403, KBM803 (manufactured by Shin-Etsu Chemical Co., Ltd.) Product name).

  The positive photosensitive resin composition according to the present invention is used by dissolving the above-described components in a solvent and forming a varnish. As the solvent, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, 2-methoxyethanol, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol acetate, cyclohexanone, cyclopentanone, tetrahydrofuran, etc. May be.

[Method for producing patterned cured film]
The method for producing a cured pattern film according to the present invention includes a step of applying and drying the positive photosensitive resin composition described above on a support substrate, a step of exposing, and an exposed portion of the photosensitive resin film after the exposure. The desired heat-resistant polymer pattern can be obtained through a step of developing with an aqueous alkali solution and a step of heat-treating the photosensitive resin film after the development. Hereinafter, each step will be described.

(Coating / drying process)
First, in the step of applying the above-described positive photosensitive resin composition onto a support substrate and drying, on a support substrate such as a glass substrate, a semiconductor, a metal oxide insulator (eg, TiO ₂ , SiO ₂ ), or silicon nitride. In addition, the positive photosensitive resin composition is spin-coated using a spinner or the like and then dried using a hot plate, an oven, or the like. Thereby, the photosensitive resin film which is a film of a positive photosensitive resin composition is formed.

(Exposure process)
Next, in the exposure step, exposure is performed by irradiating the photosensitive resin film formed on the support substrate with an actinic ray such as an ultraviolet ray, visible ray, or radiation via a mask.

(Development process)
In the development step, the pattern resin film is obtained by removing the exposed portion irradiated with actinic rays with a developer. Preferred examples of the developer include aqueous alkali solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide. The base concentration of these aqueous solutions is preferably 0.1 to 10% by weight. Furthermore, alcohols and surfactants can be added to the developer and used. Each of these can be blended in the range of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the developer.

(Heat treatment process)
Next, in the heat treatment step, the obtained pattern resin film is subjected to a heat treatment at 280 ° C. or less, preferably 250 ° C. or less, more preferably 200 ° C. or less to form a heat resistant polymer pattern. In the present invention, sufficient film properties can be obtained even when the heat treatment is performed at 200 ° C. or lower, preferably 150 to 200 ° C.

  The heat treatment is performed using a quartz tube furnace, a hot plate, rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace, or the like. In addition, either air or an inert atmosphere such as nitrogen can be selected. However, it is preferable to perform the treatment under nitrogen because the oxidation of the photosensitive resin composition film can be prevented. Since the said heating temperature range is lower than the conventional heating temperature, the damage to a support substrate or a device can be restrained small. Therefore, by using the pattern manufacturing method of the present invention, devices can be manufactured with high yield. It also leads to energy savings in the process.

  In the positive photosensitive resin composition of the present invention, the time for heat curing in the heat treatment step is a time until the remaining solvent and volatile components are sufficiently scattered, but approximately 5 hours in consideration of work efficiency. It is as follows. Moreover, the atmosphere of heat processing can also select any in air | atmosphere or inert atmosphere, such as nitrogen.

[Electronic parts]
Next, the electronic component according to the present invention will be described. The positive photosensitive resin composition of the present invention can be used for electronic parts such as semiconductor devices and multilayer wiring boards. Specifically, it can be used for forming a surface protective film of an electronic component such as a semiconductor device, an interlayer insulating film, a rewiring layer, an interlayer insulating film of a multilayer wiring board, and the like. The electronic component according to the present invention includes a semiconductor device, a multilayer wiring board, various electronic devices, and the like. In particular, a magnetoresistive memory (MRAM, Magnetoresistive Random Access Memory), a DRAM, or a flash memory is preferable. Further, the electronic component according to the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed using the positive photosensitive resin composition, and can have various structures.

  Hereinafter, based on an Example and a comparative example, it demonstrates further more concretely about this invention. In addition, this invention is not limited to the following Example.

(Measurement conditions of weight average molecular weight by GPC method)
Measuring device; Detector: L4000 UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
C-R4A Chromatopac manufactured by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 Eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / l), H ₃ PO ₄ (0.06 mol / l)
Flow rate: 1.0 ml / min, detector: UV 270 nm
The measurement was performed using a solution of 1 ml of a solvent [THF / DMF = 1/1 (volume ratio)] with respect to 0.5 mg of the polymer.

Synthesis Example 1 Synthesis of Polybenzoxazole Precursor I In a 0.2 liter flask equipped with a stirrer and a thermometer, 60 g of N-methylpyrrolidone was charged and 2,2-bis (3-amino-4-hydroxy After adding 10.4 g of phenyl) hexafluoropropane and stirring and dissolving at room temperature, 8.02 g of dodecanedioic acid dichloride was added dropwise over 10 minutes while maintaining the temperature of the reaction solution at −10 to 0 ° C. 0.125 g of 4,6-triaminopyrimidine was added and stirring was continued for 60 minutes at room temperature. The obtained reaction solution was poured into 2 liters of water, and the precipitate was collected and washed three times with pure water, to obtain a polybenzoxazole precursor (hereinafter referred to as polymer I). The polymer I had a weight average molecular weight of 28,600 and a dispersity of 1.7 determined by GPC standard polystyrene conversion.

(Synthesis Example 2) Synthesis of Polybenzoxazole Precursor II The same synthesis was performed by replacing 2,4,6-triaminopyrimidine in Synthesis Example 1 with 1,3,5-benzenetricarboxylic acid chloride. The resulting polymer is referred to as Polymer II. The weight average molecular weight calculated | required by GPC method standard polystyrene conversion of the polymer II was 45,200, and dispersion degree was 2.1.

Synthesis Example 3 Synthesis of Polybenzoxazole Precursor III The same synthesis was performed by replacing 2,4,6-triaminopyrimidine in Synthesis Example 1 with 3,4,4′-triaminodiphenyl ether. The resulting polymer is referred to as Polymer III. The weight average molecular weight of the polymer III determined by GPC standard polystyrene conversion was 26,600, and the degree of dispersion was 5.6.

Synthesis Example 4 Synthesis of Polybenzoxazole Precursor IV In a 0.5 liter flask equipped with a stirrer and a thermometer, 15.48 g (60 mmol) of 4,4′-diphenyl ether dicarboxylic acid, 90 g of N-methylpyrrolidone After cooling the flask to 5 ° C., 23.9 g (120 mmol) of thionyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of 4,4′-diphenyl ether tetracarboxylic acid chloride. Next, 87.5 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 18.30 g (50 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added. After adding and dissolving with stirring, 9.48 g (120 mmol) of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., a solution of 4,4′-diphenyl ether dicarboxylic acid chloride was added dropwise over 30 minutes, and then 30 Stirring was continued for a minute. The obtained reaction solution was poured into 3 liters of water, and the precipitate was collected, washed three times with pure water, and then dried under reduced pressure to obtain polyhydroxyamide (hereinafter referred to as polymer IV). The polymer IV had a weight average molecular weight of 16,200 and a dispersity of 1.8 determined by GPC standard polystyrene conversion.

(Examples 1-11 and Comparative Examples 1-5) (Chemical resistance)
(B) Component AZ Materials (2- (4-hydroxyphenyl) -2- [4- [1,1- (4) with respect to 100 parts by weight of the polybenzoxazole precursor as component (a). 11 parts by weight of a naphthoquinodiazide-5-sulfonic acid ester compound of hydroxyphenyl) ethyl] phenyl], and (c) a crosslinking agent as component (A (TML-BPAF): 7.5 parts by weight, B ( TML-BPAP): 6.75 parts by weight, C (DML-MBOC): 5.5 parts by weight, D (MX-290) 5.23 parts by weight, E (MX-270) 4.87 parts by weight, (d ) 163 parts by weight of the solvent BLO / PGMEA (9: 1), 2.9 parts by weight of Gelest (bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane) as a further additive component, That To obtain a positive photosensitive resin composition. Table 1 shows the types of the polymers I to IV which are the components (a) and the crosslinking agents A to E which are the components (c) in Examples 1 to 11 and Comparative Examples 1 to 5.

In addition, A, B, C, D, and E of the component (c) are represented by the following structural formulas (24) to (28), respectively.

  This positive photosensitive resin composition solution was spin-coated on a silicon wafer and heated at 120 ° C. for 3 minutes to form a coating film having a thickness of 15 μm. Thereafter, the coating film was heated in an inert gas oven at 200 ° C. for 1 hour in a nitrogen atmosphere to obtain a cured film. Furthermore, the change of the cured film was observed when each cured film was deposited on acetone, NMP: N-methylpyrrolidone, PGMEA: propylene glycol monomethyl ether acetate, and BLO: γ-butyrolactone at room temperature for 15 minutes. The results are shown in Table 1 above. In Table 1, those with cracks in the cured film were marked with ×, and those without cracks were marked with ○.

  Separately, the obtained film was immersed in a hydrofluoric acid aqueous solution together with the silicon wafer, the cured film was peeled off from the silicon wafer, washed with water and dried, and then measured for elongation at break (measured with a tensile tester). The results of elongation at break in each Example and Comparative Example are shown in Table 1 above.

  As is apparent from Table 1, Examples 1 to 11 showed excellent chemical resistance against all of acetone, BLO, and NMP even when cured at 200 ° C. Moreover, in the polymers of Examples 1-11, it turned out that the cured film at 200 degrees C or less is comparable to comparative examples 1-5 also in breaking elongation.

(Photosensitive characteristic evaluation)
(B), (c) component and other additive components are blended in the predetermined amounts shown above with respect to 100 parts by weight of the polybenzoxazole precursor as the component (a), and a solution of the photosensitive resin composition Got.

  Regarding Examples 1 to 11, the sensitivity was good and pattern formation was possible. Further, when the component (b) was not added to the formulation, pattern formation could not be performed and sufficient photosensitive characteristics could not be obtained.

  As described above, the photosensitive resin composition of the present invention, Examples 1 to 11 are 200 ° C. or less compared to Comparative Examples 1 to 5, and thus the elongation in curing and chemical resistance are compared with the cured film when cured at a high temperature. However, film properties comparable to those obtained were obtained.

  As described above, the positive-type photosensitive resin composition for low-temperature curing using the branched polymer as a base resin according to the present invention is cured at a high temperature even after curing at a low temperature of 200 ° C. or lower. Performance comparable to that obtained. In particular, the solvent resistance to various chemicals is very excellent. Moreover, according to the method for producing a cured pattern film of the present invention, by using the positive photosensitive resin composition, a pattern having a good shape can be obtained even in a low temperature curing process with excellent sensitivity, resolution, and adhesiveness. Since it has a good shape and pattern and can be cured by a low-temperature process, damage to the device can be avoided and a highly reliable electronic component can be obtained. Therefore, it is useful for an electronic component such as an electronic device, and is particularly suitable for a magnetoresistive memory.

Claims (12)

A positive-type photosensitive resin composition for low-temperature curing used for forming a cured film by heat treatment at 280 ° C. or lower, (a) polybenzoxazole (PBO), polyimide (PI) having a branched structure Or a precursor thereof, (b) a compound capable of generating an acid by light, and (c) a compound that can be crosslinked with the component (a) by heat or polymerized by itself. A positive photosensitive resin composition for low-temperature curing.   The component (a) is a polyvalent amine having 3 or more amino groups, a polyhydric acid anhydride having 3 or more anhydride groups, a carboxyl group or 3 or more functional groups derived from a carboxyl group. It is synthesized using at least one compound selected from the group consisting of polyvalent carboxylic acids or polyvalent carboxylic acid derivatives having a polyvalent isocyanate having three or more isocyanate groups. 1. A positive photosensitive resin composition for low-temperature curing according to 1.   The positive photosensitive resin composition for low-temperature curing according to claim 1, wherein the component (a) has a fatty chain.   The positive photosensitive resin composition for low-temperature curing according to any one of claims 1 to 3, wherein the component (b) is an o-quinonediazide compound.   The positive photosensitive resin composition for low-temperature curing according to claim 1, wherein the component (c) is a compound having at least one methylol group or alkoxyalkyl group in the molecule.   The positive-type photosensitive resin composition for low-temperature curing according to claim 1, wherein the component (c) is a compound represented by the following general formula (1).

(Wherein X represents a single bond or a monovalent to tetravalent organic group, R ¹ And R ² Each independently represents a hydrogen atom or a monovalent organic group, a is an integer of 1 to 4, and b and c are each independently an integer of 0 to 4. )   The positive photosensitive resin composition for low-temperature curing according to claim 1, wherein the component (c) is a compound represented by the following general formula (2).

(In the formula, two Y's are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group containing an oxygen atom or a fluorine atom in a part thereof; ^Three ~ R ⁶ Each independently represents a hydrogen atom or a monovalent organic group, d and e are each independently an integer of 1 to 3, and f and g are each independently an integer of 0 to 4. )   The positive photosensitive resin composition for low-temperature curing according to claim 1, wherein the component (c) is a compound represented by the following general formula (3).

(Wherein a plurality of R ⁷ And R ⁸ Each independently represents a hydrogen atom or a monovalent organic group, R ^{8 '} Is a divalent organic group. )   The photosensitive resin film formation which forms the photosensitive resin film by apply | coating the positive photosensitive resin composition for low temperature curing of any one of Claims 1-8 on a support substrate, and drying. A step of exposing the photosensitive resin film to a predetermined pattern, a developing step of developing the exposed photosensitive resin film using an alkaline aqueous solution to obtain a patterned resin film, and the pattern after development And a heat treatment step of obtaining a pattern cured film by heat-treating the resin film at a temperature of 280 ° C. or lower.   The method for producing a cured pattern film according to claim 9, wherein the heat treatment temperature is 200 ° C. or lower in the step of heat-treating the developed pattern resin film.   A pattern cured film obtained by the method for producing a pattern cured film according to claim 9 or 10 is provided as at least one selected from the group consisting of an interlayer insulating film layer, a rewiring layer, and a surface protective film layer. Electronic parts characterized by   The electronic component according to claim 11, wherein the electronic component is a magnetoresistive memory.