JP2008033158A - Positive photosensitive resin composition, method for producing patterned cured film, and electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition which satisfies both of good photosensitive characteristics and cured film properties, a method for producing a patterned cured film and electronic components. <P>SOLUTION: A semiconductor substrate 1 on which a first conductor layer 3, a second conductor layer 7 and an interlayer insulation film 4 have been formed is spin-coated with the positive photosensitive resin composition. This composition is dried and irradiated with light through a mask having a pattern for forming a window 6C in a predetermined part, and after development with an alkaline aqueous solution, heating (curing) is carried out to form a surface protective film layer 8. The positive photosensitive resin composition comprises (a) a polymer component consisting of two or more different heat-resistant polymers each having a reactive end group and (b) a compound which generates an acid upon irradiation with active light. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a positive photosensitive resin composition, a method for producing a patterned cured film, and an electronic component. More specifically, the present invention relates to a heat-resistant positive photosensitive resin composition containing a photosensitive heat-resistant polymer, The present invention relates to a method for producing a patterned cured film using a stencil 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, as semiconductor elements have been highly integrated and increased in size, 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. Thus, 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 above negative type requires an organic solvent such as N-methylpyrrolidone for development, a positive photosensitive resin that can be developed with an aqueous alkaline solution has recently been 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 a soluble polyimide via an ester bond (for example, see Non-Patent Document 2), and a method in which naphthoquinone diazide is mixed into a polyimide precursor (for example, see Patent Document 15) )and so on.

  However, the negative type has a problem in resolution due to its function, and in some applications, there is a problem in that the yield in manufacturing is reduced. 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 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, amine end groups sealed with a polymerizable group (see, for example, Patent Documents 20 to 22) have also been proposed. As a diazoquinone compound containing a large number of aromatic rings is used, the sensitivity is low, and it is necessary to increase the amount of diazoquinone compound added. It 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, a method using a negative chemical amplification system using a crosslinking reaction that proceeds in the presence of an acid catalyst (see, for example, the above-mentioned Patent Documents 17 and 31) has been proposed. A hydroxyl group serves as a cross-linking point. Actually, the cross-linking reaction efficiency is low and the sensitivity is not high.

  Furthermore, in addition to the above, the photosensitive resin composition is required to be compatible with cured film characteristics. As an example, the requirement for low thermal expansion will be described. The diameter of the silicon wafer that becomes the substrate increases year by year, and the problem of warping of the silicon wafer formed with polyimide or polybenzoxazole as a surface protection film becomes larger due to the difference in thermal expansion coefficient between polyimide and silicon wafer. is doing. For this reason, there is a strong demand for a photosensitive material having a lower thermal expansibility than before. Generally, low thermal expansion can be achieved by making the molecular structure rigid. However, in the case of the rigid structure, there is a problem that the i-line is hardly transmitted and the photosensitive property is lowered. Thus, it is extremely difficult to satisfy not only the low thermal expansion property but also the cured film property and the photosensitive property at the same time.

Japanese Patent Laid-Open No. 49-11541 Japanese Patent Laid-Open No. 50-40922 JP 54-145794 A JP-A-56-38038, etc. 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 Japanese Examined Patent Publication No. 64-60630 US Pat. No. 4,395,482 JP 52-13315 A JP-A-1-46862 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 2000-56559 A JP 2001-194791 A JP 2002-526793 A US Pat. No. 6,143,467 JP 2001-125267 A J. et al. Macromol. Sci. Chem. , A24, 10, 1407, 1987 Macromolecules, 23, 4796, 1990

  This invention is made | formed in view of the said situation, The subject is providing the positive type photosensitive resin composition which makes a photosensitive characteristic and a cured film characteristic compatible.

  In addition, the present invention provides a method for producing a patterned cured film that can be developed with an alkaline aqueous solution by using the photosensitive resin composition and that can obtain a patterned cured film having a good shape excellent in heat resistance and mechanical properties. This is the issue. Furthermore, this invention makes it a subject to provide the electronic component which has high reliability by having a pattern cured film of a favorable shape and characteristic.

  In order to solve the above problems, a positive photosensitive resin composition according to the present invention comprises (a) a polymer component comprising two or more different heat-resistant polymers having reactive end groups, and (b) actinic ray irradiation. And a compound capable of generating an acid.

  In the positive photosensitive resin composition of the present invention, at least one of the polymer components (a) is polyimide, polyoxazole, polyamideimide, polyamide, polyamic acid, polyamic acid ester, polyhydroxyamide, respectively. And a heat-resistant polymer compound selected from the group consisting of these copolymers.

  The positive photosensitive resin composition of the present invention is characterized in that at least one of the polymer components (a) is soluble in an alkaline aqueous solution.

  Moreover, in the positive photosensitive resin composition of the present invention, in addition to the (a) polymer component and the (b) component, (c) the end group of at least one polymer of the (a) polymer component by heat. It contains the compound which can be bridge | crosslinked with.

  In the positive photosensitive resin composition of the present invention, at least one of the components (a) is selected from the group consisting of primary or secondary alcohols, carboxyl groups, amino groups, thiols, phenols and aromatic rings. And the component (c) is a methyl ether, an alkoxyalkyl group, a tertiary alcohol, a cycloalkyl group, an olefin, a triple bond, a halogenated alkyl, an epoxy group or other cyclic ether, an ester bond, It contains a functional group or bond selected from the group consisting of carbonate and isocyanate.

  In the positive photosensitive resin composition of the present invention, at least one of the components (a) is methylol, alkoxyalkyl group, tertiary alcohol, cycloalkyl group, olefin, triple bond, alkyl halide, epoxy. A functional group or bond selected from the group consisting of cyclic ethers such as groups, ester bonds, carbonates and isocyanates, and the component (c) is a primary or secondary alcohol, carboxyl group, amino group, thiol, It comprises a functional group or bond selected from the group consisting of phenol and aromatic rings.

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

  In the positive photosensitive resin composition of the present invention, 0.01 to 50 parts by weight of the component (b) and (c) with respect to 100 parts by weight of the total amount of the (a) polymer component. It contains 0.1 to 50 parts by weight of the component.

  In addition, the method for producing a patterned cured film of the present invention includes a photosensitive resin film forming step in which the positive photosensitive resin composition is applied on a support substrate and dried to form a photosensitive resin film, and the photosensitive resin is formed. An exposure step of exposing the film, a development step of developing the exposed photosensitive resin film using an aqueous alkaline solution to obtain a patterned resin film, and a heat treatment of the patterned resin film to obtain a patterned cured film A heat-solidifying step.

  The electronic component of the present invention is an electronic component having an electronic device having a layer of a patterned cured film obtained by the method for producing a patterned cured film, wherein the pattern curing is performed in the electronic device. The film layer is provided as an interlayer insulating film layer and / or a surface protective film layer.

  By using the positive photosensitive resin composition of the present invention, it is possible to form a cured pattern film having excellent sensitivity and resolution. In addition, a patterned cured film obtained by patterning and heat-curing the positive photosensitive resin composition of the present invention by blending and using a resin excellent in photosensitive characteristics and a resin excellent in cured film characteristics is excellent in heat resistance and mechanical characteristics. Can be. Further, by adding a resin having characteristics such as low thermal expansion, high elasticity, and low elasticity, these characteristics can be arbitrarily expressed in addition to the photosensitive characteristics and heat resistance.

  Moreover, according to the method for producing a cured pattern 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, the electronic component of the present invention has an effect of high reliability by having a patterned cured film having a good shape and characteristics.

  Embodiments of a positive photosensitive resin composition, a method for producing a patterned cured film, and an electronic component according to the present invention will be described below in detail with reference to the drawings. In addition, this invention is not limited by this embodiment.

[Photosensitive resin composition]
First, the positive photosensitive resin composition according to the present invention will be described.
The positive photosensitive resin composition according to the present invention comprises (a) a polymer component composed of two or more different heat-resistant polymers having reactive end groups (hereinafter simply referred to as “component (a)”), b) A compound that generates an acid upon irradiation with actinic rays (hereinafter, simply referred to as “component (b)”). Hereinafter, each component will be described.

[(A) component]
The component (a) in the present invention comprises two or more types of heat resistant polymers. Examples of the heat resistant polymer include polyimide, polyoxazole, polyamideimide, polyamide, polyamic acid, polyamic acid ester, polyhydroxyamide, and the like. In addition, at least one of the component (a) is selected from polyimide, polyoxazole, polyamideimide, polyamide, polyamic acid, polyamic acid ester, polyhydroxyamide, and copolymers thereof, processability and heat resistance. This is preferable. Further, at least one of the component (a) is preferably a polymer that is soluble in an aqueous alkali solution from the viewpoint of developability in the aqueous alkali solution.

  The alkaline aqueous solution is an alkaline solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution, a metal hydroxide aqueous solution, or an organic amine aqueous solution. In general, since an aqueous tetramethylammonium hydroxide (TMAH) solution having a concentration of 2.38% by weight is used, it is preferable that at least one of the components (a) is soluble in this aqueous solution.

In addition, one reference | standard that (a) component of this invention is soluble in aqueous alkali solution is demonstrated below.
Spin coating of varnish (resin solution) obtained by dissolving component (a) alone or in any solvent together with component (b) and component (c) described below in order on a substrate such as a silicon wafer Thus, a coating film having a film thickness of about 5 μm is formed. This is immersed in any one of tetramethylammonium hydroxide aqueous solution, metal hydroxide aqueous solution, and organic amine aqueous solution at 20 to 25 ° C. As a result, when it can be dissolved as a uniform solution, it is determined that the component (a) is soluble in an alkaline aqueous solution.

  There are no particular restrictions on the combination of the polymers of the component (a) used in two or more types. For example, at least one of them is excellent in developability and photosensitive characteristics, and the other is excellent in cured film characteristics. If it is selected, it is possible to achieve both photosensitive characteristics and cured film characteristics, which is preferable. Similarly, by combining a polymer having two or more different cured film characteristics, both characteristics can be expressed together. For example, a combination of a polymer excellent in low thermal expansion and a polymer excellent in mechanical properties, a combination of a polymer excellent in heat resistance and a polymer excellent in mechanical properties, and the like can be given as preferable examples.

  The reactive terminal group of the component (a) connects the constituent polymers of the component (a) by connecting each other or via the component (c) described later. Thereby, each characteristic which the constituent polymer of the component (a) has can be expressed more strongly and a synergistic effect can be achieved such as improvement in mechanical strength.

  Examples of the reactive terminal group include alcohol, carboxyl group, amino group, thiol, aromatic ring, methylol, alkoxyalkyl group, cycloalkyl group, olefin, triple bond, halogenated alkyl, epoxy group, and other cyclic ethers and ester bonds. , Carbonate, isocyanate and the like are preferable, but not limited thereto.

  The polymer soluble in an alkaline aqueous solution that can be used as the component (a) will be further described. Polyimide can be obtained, for example, by reacting tetracarboxylic dianhydride and diamine and dehydrating and ring-closing. Polyoxazole can be obtained, for example, by reacting dicarboxylic acid dichloride and dihydroxydiamine, followed by dehydration and ring closure. Polyamideimide can be obtained, for example, by reacting tricarboxylic acid and diamine and dehydrating and ring-closing. Polyamide can be obtained, for example, by reacting dicarboxylic acid dichloride with diamine. The polyamic acid can be obtained, for example, by reacting tetracarboxylic dianhydride and diamine. The polyamic acid ester can be obtained, for example, by reacting a tetracarboxylic acid diester dichloride with a diamine.

  In the polymer that can be used as the component (a), examples of polymers that are excellent in developability (photosensitive characteristics) and polymers that are excellent in cured film characteristics will be described.

  Among the above-mentioned polymers that are soluble in an alkaline aqueous solution, polyhydroxyamide that can be ring-closed to polybenzoxazole by heating is excellent in heat resistance, mechanical properties, and electrical properties in addition to developability for alkaline aqueous solutions. Therefore, it is being used frequently. Therefore, this polyhydroxyamide can be preferably used as a polymer component excellent in developability (photosensitive characteristics) in the present invention. This polyhydroxyamide has a repeating unit represented by the following general formula (1). 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 during curing.

（式中、Ｕは４価の有機基を示し、Ｖは２価の有機基を示す）

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

The polyhydroxyamide having a repeating unit represented by the general formula (1) that can be used in the present invention may have the repeating unit, but the solubility of the polyhydroxyamide in an alkaline aqueous solution is a phenolic hydroxyl group. Therefore, it is preferable that an amide unit containing a hydroxy group is contained in a certain proportion or more.
That is, the following formula (2)

（式中、Ｕは４価の有機基を示し、ＶとＷは２価の有機基を示す。ｊとｋは、モル分率を示し、ｊとｋの和は１００モル％であり、ｊが６０〜１００モル％、ｋ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ｊとｋのモル分率は、ｊ＝８０〜１００モル％、ｋ＝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, j and k represent a mole fraction, and the sum of j and k is 100 mol%, j Is 60 to 100 mol%, and k is 40 to 0 mol%.)
It is preferable that it is polyhydroxyamide represented by these. Here, the molar fraction of j and k in the formula is more preferably j = 80 to 100 mol% and k = 20 to 0 mol%.

  In the present invention, the polyamide having a repeating unit represented by the general formula (1) can be generally synthesized from a dicarboxylic acid derivative and a hydroxy group-containing diamine. Specifically, a polyamide having a repeating unit represented by the general formula (1) can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting with the diamine. 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, those used in usual acid chlorideation reaction of carboxylic acid, for example, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride and the like can be used.

  The dichloride derivative can be synthesized by reacting the dicarboxylic acid derivative and the halogenating agent in a solvent or by 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 general formulas (1) and (2), the tetravalent organic group represented by U is generally an amine having two hydroxy groups that react with a dicarboxylic acid to form a polyamide structure. A residue of a diamine having a structure located in the ortho position, preferably a tetravalent aromatic group, preferably having 6 to 40 carbon atoms, and a tetravalent aromatic group having 6 to 40 carbon atoms Is more preferable. 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 general formula (2), the divalent organic group represented by W is generally a diamine residue that reacts with a dicarboxylic acid to form a polyamide structure, and forms the U. And a divalent aromatic group or aliphatic group is preferred, and those having 4 to 40 carbon atoms are preferred, and divalent aromatic groups having 4 to 40 carbon atoms are more preferred.

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 general formulas (1) and (2), the divalent organic group represented by V is a dicarboxylic acid residue that reacts with diamine to form a polyamide structure and is a divalent aromatic group. A group having 6 to 40 carbon atoms is preferable, and a divalent aromatic group having 6 to 40 carbon atoms is more preferable. As the divalent aromatic group, those in which two bonding sites are both present on the aromatic ring are preferred.

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, Aliphatic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, oxalic acid, malonic acid and succinic acid While such carbon acid but not limited thereto.
These compounds can be used alone or in combination of two or more.

  The polymer that can be used as the component (a) is not particularly limited as long as it can be expected to improve the cured film properties, but it is preferable to use polyamic acid, polyamic acid ester, or polyhydroxyamide from the viewpoint of compatibility.

  Preferred polyamic acid and polyamic acid ester will be described in the following general formula (3).

（式中、Ｒ¹：四価の有機基、Ｒ²：二価の有機基、Ｒ³：独立に水素または一価の有機基を示す。）

(In the formula, R ^{1 is a} tetravalent organic group, R ^{2 is} a divalent organic group, and R ^{3 is} independently hydrogen or a monovalent organic group.)

As a structure excellent in low thermal expansibility and high elastic modulus, the tetravalent organic group represented by R ¹ in the general formula (3) includes benzene, biphenyl, naphthalene, benzophenone, cyclobutane, cyclohexane, xanthene, thio Xanthene and the like. Examples of the divalent organic group represented by R ² include benzene, biphenyl, benzophenone, and cyclohexane. Note that these skeletons may be substituted with a methyl group, a trifluoromethyl group, a fluorine atom, a hydroxyl group, or the like, or a plurality thereof may be used in combination.

In order to realize a structure having a low elastic modulus, examples of the tetravalent organic group represented by R ¹ in the general formula (3) include diphenyl ether, diphenylmethane, diphenylpropane, and diphenylhexafluoropropane. . Examples of the divalent organic group represented by R ² include diphenyl ether, diphenylmethane, diphenylpropane, and diphenylhexafluoropropane. Note that these skeletons may be substituted with a methyl group, a trifluoromethyl group, a fluorine atom, or the like. Moreover, what has a siloxane bond can also be mentioned as a preferable thing. These may be used in combination.

The monovalent organic group represented by R ³ in the structural unit represented by the general formula (3) does not depend on the properties to be imparted. Specifically, an aliphatic or aromatic hydrocarbon group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a phenyl group, or a benzyl group, and a fluorine-containing group. Typical examples include alkoxyalkyl groups having 2 to 10 carbon atoms, such as methoxyethyl group, and those containing fluorine, but are not limited thereto. Of these, preferred groups include an ethyl group, a 2,2,2-trifluoroethyl group, an isopropyl group, a t-butyl group, and a benzyl group.

Both the polyamic acid and the polyamic acid ester exemplified above have generally good heat resistance and mechanical properties. More preferably, R ¹ and R ² are aromatic for improving heat resistance and breaking strength. In order to improve the elongation at break using a skeleton of the system, an alicyclic skeleton, a fatty hydrocarbon, or a skeleton having an ether bond is used.

  A preferred polyhydroxyamide will be described in the following general formula (1).

（式中、Ｕは４価の有機基を示し、Ｖは２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 order to realize a structure excellent in low thermal expansion and high elastic modulus, examples of the divalent organic group represented by U in the general formula (1) include benzene, biphenyl, benzophenone, xanthene, and thioxanthene. . Examples of the divalent organic group represented by V include benzene, biphenyl, benzophenone, and cyclohexane. Note that these skeletons may be substituted with a methyl group, a trifluoromethyl group, a fluorine atom, or the like, or a plurality thereof may be used in combination.

In order to realize a structure having a low elastic modulus, examples of the tetravalent organic group represented by the general formula U include diphenyl ether, diphenylmethane, diphenylpropane, and diphenylhexafluoropropane. Examples of the divalent organic group represented by R ² include diphenyl ether, diphenylmethane, diphenylpropane, diphenylhexafluoropropane, methane, ethane, propane, butane, and pentane. Moreover, the oxalic acid residue in which V became a single bond can also be mentioned. Note that these skeletons may be substituted with a methyl group, a trifluoromethyl group, a fluorine atom, or the like. Moreover, what has a siloxane bond can also be mentioned as a preferable thing. These may be used in combination.

  All of the polyhydroxyamides exemplified above have generally good heat resistance and mechanical properties. More preferably, in order to improve heat resistance and breaking strength, an aromatic skeleton is added to U and V. In order to improve the elongation at break, an alicyclic skeleton, a fatty hydrocarbon, or a skeleton having an ether bond is used.

  In the component (a) used in the present invention, the ratio of the terminal group to the repeating unit is a molar ratio and is a repeating unit with respect to the terminal group 2 (for example, in the case of polyimide or polyamide, an acid residue and an amine residue). (Repeating unit) 1 to 100 is preferable, and 2 to 50 is more preferable. If the terminal group ratio is smaller than this, the effect of the crosslinking reaction may be diminished, or the photosensitivity may be deteriorated. On the contrary, when the ratio is larger than this, even if the crosslinking reaction sufficiently proceeds due to the decrease in the molecular weight, there is a possibility that sufficient film properties cannot be obtained.

In the case of using polyimide, polyoxazole, polyamideimide, polyamide, polyamic acid, polyamic acid ester, polyhydroxyamide as the component (a), the molar ratio of acid residue to amine residue is not particularly limited, but the terminal group is amino. When attributed to phenol, the acid residue is one more than the amine residue, preferably in the range of 100: 99 to 2: 1, and more preferably in the range of 50:49 to 3: 2. When the terminal group is a hydroxybenzoic acid derivative, the acid residue is less than the amine residue, preferably in the range of 99: 100 to 1: 2, and in the range of 49:50 to 2: 3. Is more preferable. The quantitative method can be performed by ¹ H NMR measurement.

  The molecular weight of the polymer constituting 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 molecular weight is a value obtained by measuring by a gel permeation chromatography method and converting from a standard polystyrene calibration curve.

[Component (b)]
In the positive photosensitive resin composition of the present invention, a compound that generates an acid upon irradiation with actinic rays (hereinafter referred to as an acid generator) is used as the component (b) together with the polymer used as the component (a). The content of the acid generator is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of component (a) in order to improve the sensitivity and resolution during exposure. It is more preferably 20 parts by weight, and further preferably 0.5 to 20 parts by weight.

  The acid generator (compound of component (b)) used in the positive photosensitive resin composition of the present invention has a function of increasing the solubility of the light irradiated part in an alkaline aqueous solution. However, it is preferable that the terminal groups of the component (a) or the terminal groups of the component (a) and the functional group of the component (c) do not cause a bond (crosslinking) due to the acid generated. Examples of the type include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, and the like. Although there is no particular limitation, the o-quinonediazide compound has high sensitivity, and the end group of the component (a) Since the functional group of the component (c) 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 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 dehydrochlorination agent include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like.

[Component (c)]
In the positive photosensitive resin composition of the present invention, in addition to the components (a) and (b) (acid generator), an object is to improve the performance of cured film properties and to improve the difference in dissolution rate depending on the presence or absence of light irradiation. In addition, as the component (c), a compound capable of crosslinking with the terminal group of at least one polymer of the component (a) by heat can be used in combination. The temperature at which 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 crosslinking reaction of the component (a) and the component (c) in the present invention is not necessarily limited to the crosslinking point only at the terminal, and together with this, the functional group in the main chain of the component (a) and (c) The crosslinking reaction of the components may proceed.

  As a combination of the terminal group of component (a) and the functional group of component (c), a bond is formed between the two in the form of a covalent bond, an ionic bond, or a hydrogen bond by heat in the presence of an acid. There is no particular limitation as long as it is born.

  From the viewpoint of the mechanical properties of the finally obtained film, a combination in which the functional groups and bonds of the component (a) and the component (c) are each selected from the following groups A and B is preferable. In this case, the component (a) may be selected from either group, but in principle, the component (a) and the component (c) need to be a combination selected from different groups.

[Group A] Primary or secondary alcohol, phenol, carboxyl group, amino group, thiol, aromatic ring.
[Group B] Cyclic ethers such as methylol, alkoxyalkyl groups, tertiary alcohols, cycloalkyl groups, olefins, triple bonds, alkyl halides, epoxy groups, ester bonds, carbonates, isocyanates.

  However, even in combinations not corresponding to the above, carboxyl groups or esters and amino groups, carboxyl groups or esters and primary or secondary alcohols, cycloalkyl groups, carboxyl groups, alcohols, epoxy groups, olefins or triple bonds Further, methylols can also be mentioned as preferable combinations having high reactivity.

  When the polymer exemplified as the preferred component (a) is used, the end of component (a) is derived from a carboxyl group or an ester, phenol, amino group or derived from the carboxyl group or from the viewpoint of ease of introduction of the end group. It is desirable to be an isocyanate precursor. From this point of view, as a particularly preferable combination, (a) component is phenol, (c) component is methylol, tertiary alcohol, (a) component is carboxyl group or ester, and (c) component is primary or 2 A combination of a secondary alcohol, an epoxy group, a vinyl ether or an isocyanate, an amino group as the component (a), a combination of an epoxy group, a carboxyl group or an ester as the component (c), an isocyanate as the component (a), ( As a component c), a combination with a primary or secondary alcohol, phenol, carboxyl group or ester can be mentioned.

  In addition, (a) component and (c) component are olefins or triple bonds, or (a) component is phenol, (c) component is methylol, alkoxyalkyl group in terms of a combination that provides good cured film strength. A combination with a tertiary alcohol or vinyl ether, an amino group or isocyanate as the component (a), and a combination of a carboxyl group or an ester as the component (c) are particularly preferable.

  The combination of the terminal group of the component (a) and the functional group of the component (c) is basically a combination that does not cause bonding (crosslinking) when the photosensitive resin composition is applied. That is, the temperature at which crosslinking occurs in the combination is preferably 150 ° C. or higher in the absence of acid. Therefore, each functional group listed as an example of the combination so far is made latent by a method such as a protective group or a derivative, etc., and desired by a photochemical reaction due to exposure or a chemical change due to heat in a subsequent post-exposure heating step. A technique such as conversion to a functional group can also be taken. For example, since isocyanate reacts even at a low temperature of 150 ° C. or lower, it can be introduced into the terminal group of component (a) or component (c) in a precursor state in which an amino group is blocked with an alkoxycarbonyl group or the like. it can.

  Preferred as the component (c) are two or more methylol groups, alkoxymethyl groups, epoxy groups, oxetanes, vinyl ether groups, olefins, alkynyl groups, cyano groups, hydroxy groups, carboxyl groups, ester bonds, cyclohexanes in the molecule. The compound which has a functional group applicable to what is preferable in combination with (a) component illustrated previously, such as an alkyl group, an amino group, an isocyanate group, can be mentioned. Particularly preferred are compounds in which these substituents are substituted on the aromatic ring, namely phenols, bisphenols, polyphenols, novolac resins, resole resins, and melamine, benzoguanamine, glycoluril, urea compounds in which the N-position is substituted with these substituents. preferable. Examples of these preferable compound groups are given as the following general formulas (4) and (5), but the present invention is not limited to these.

（式中、Ｘは単結合、または１〜４価の有機基を示し、Ｚは（ａ）成分と反応する官能基を示し、Ｒ¹は水素原子、水酸基または一価の有機基を示し、ｎは１〜４の整数であり、ｐ、ｑは各々独立に０〜４の整数である。）

(In the formula, X represents a single bond or a 1 to 4 valent organic group, Z represents a functional group that reacts with the component (a), R ¹ represents a hydrogen atom, a hydroxyl group or a monovalent organic group, n is an integer of 1 to 4, and p and q are each independently an integer of 0 to 4.)

（式中、Ｚは各々独立に（ａ）成分と反応する官能基を示し、Ｒ²は各々独立に水素原子または一価の有機基を示し、互いが結合することで環構造となっていても良い。）

(In the formula, each Z independently represents a functional group that reacts with the component (a), each R ² independently represents a hydrogen atom or a monovalent organic group, and is bonded to each other to form a ring structure. Is also good.)

  In the general formula (4), as the organic group represented by X, an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group or a propylene group, an alkylidene group having 2 to 10 carbon atoms such as an ethylidene group, Arylene groups having 6 to 30 carbon atoms such as 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, thioether bonds, Amide bond, etc., and the following general formula (6)

（式中、個々のＸ’は、各々独立に、単結合、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、炭素数が２〜１０のもの）、それらの水素原子の一部また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り、Ｒ³は水素原子、ヒドロキシ基、アルキル基また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、ｍは１〜１０である。）
で示される２価の有機基が好ましいものとして挙げられる。さらに、下記一般式（７）に挙げられるものは、感度、解像度にも優れるため、特に好ましいものとして挙げられる。

(In the formula, each X ′ is independently a single bond, an alkylene group (for example, having 1 to 10 carbon atoms), an alkylidene group (for example, having 2 to 10 carbon atoms), A group in which part or all of the hydrogen atoms are substituted with a halogen atom, a sulfone group, a carbonyl group, an ether bond, a thioether bond, an amide bond, etc., and R ³ is a hydrogen atom, a hydroxy group, an alkyl group or It is a haloalkyl group, and when there are a plurality of them, they may be the same as or different from each other, and m is 1 to 10.)
A divalent organic group represented by the formula is preferable. Furthermore, those listed in the following general formula (7) are particularly preferable because they are excellent in sensitivity and resolution.

（式中、２つのＹは各々独立に水素原子または炭素原子数１〜１０のアルキル基であり酸素原子またはフッ素原子を含んでいても良く、Ｒ⁴〜Ｒ⁵は各々独立に水素原子または一価の有機基を示し、ｐ、ｑ、ｒおよびｓ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 or an alkyl group having 1 to 10 carbon atoms and may contain an oxygen atom or a fluorine atom, and R ^{4 to} R ⁵ are each independently a hydrogen atom or Valent organic group, p, q, r and s are each independently an integer of 0 to 4.)

  These crosslinking agents may be used alone or in combination of two or more.

  The content of the component (c) used in the present invention is 0. 0.1 parts by weight with respect to 100 parts by weight of the component (a) in order to suppress the sensitivity and resolution at the time of exposure and to prevent the pattern cured film from melting at the time of heat curing. The amount is preferably 1 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, and still more preferably 0.5 to 20 parts by weight.

[Other ingredients]
In addition to the components (a) to (c), the positive photosensitive resin composition according to the present invention comprises (d) an acid generating compound, (e) an adhesion-imparting agent, (f) a surfactant or a leveling agent. (G) You may contain a solvent etc.

[Other components: (d) Acid generating compound]
First, in order to accelerate the crosslinking reaction of component (c) at the time of thermosetting, (d) an acid generating compound that generates an acid by heat may be used in combination. The acid used as a catalyst is preferably a strong acid. Specifically, aryl acids such as p-toluenesulfonic acid and benzenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, and perafluorosulfonic acid such as nonafluorobutanesulfonic acid. Alkyl sulfonic acids such as fluoroalkyl sulfonic acids, methane sulfonic acids, ethane sulfonic acids, butane sulfonic acids are desirable. In order to generate the acid by heat, the acid generating compound is added to the positive photosensitive resin composition of the present invention in the form of a salt as an onium salt or in the form of 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, it is more preferable that the thermal decomposition starting temperature is 140 ° C. to 250 ° C., since 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.

[Other components: (e) Adhesion imparting agent]
The positive photosensitive resin composition of the present invention can contain (e) an adhesion-imparting agent such as an organic silane compound and an aluminum chelate compound in order to enhance the adhesion of the cured film to the substrate.

  Examples of the organic silane compound include vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, ureapropyltriethoxysilane, 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, isopropyldiphenyl Silanol, 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 (butyl Hydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropylhydroxysilyl) benzene, 1,4-bis (dibutylhydroxy) And silyl) benzene.

  Examples of the aluminum chelate compound include tris (acetylacetonate) aluminum, acetylacetate aluminum diisopropylate, and the like.

  When using these (e) adhesion imparting agents, it is preferable to contain 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of component (a). preferable.

[Other components: (f) 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 polymer KP341, KBM303, KBM403, KBM803 (manufactured by Shin-Etsu Chemical Co., Ltd.) Product name).

[Other components: (g) Solvent]
In the present invention, these components are dissolved in (g) a solvent and generally used in the form of a varnish (resin liquid). Such solvents include 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. It may be used.

[Method for producing patterned cured film]
Next, the manufacturing method of the pattern cured film of this invention is demonstrated. The method for producing a patterned cured film according to the present invention includes a photosensitive resin film forming step of forming the photosensitive resin film by applying the above-described positive photosensitive resin composition onto a supporting substrate and drying the photosensitive resin film, and the photosensitive resin film. An exposure step for exposing the photosensitive resin film, a developing step for developing the exposed photosensitive resin film using an alkaline aqueous solution to obtain a patterned resin film, and a patterned cured film obtained by heat-treating the patterned resin film Through the heat curing step, a desired heat-resistant polymer pattern cured film can be produced. Hereinafter, each step will be described.

(Photosensitive resin film forming process)
In the step of forming a photosensitive resin film by applying a positive photosensitive resin composition on a support substrate and drying, a glass substrate, a semiconductor, a metal oxide insulator (eg, TiO ₂ , SiO _2, etc.), silicon nitride The photosensitive resin composition described above is spin-coated using a spinner or the like on a support substrate such as. Then, the photosensitive resin film which is a film of the photosensitive resin composition is formed on a support substrate by drying using a hot plate, oven, etc.

(Exposure process)
Next, in the exposure step, the photosensitive resin composition (photosensitive resin film) formed as a film on the support substrate is irradiated with actinic rays such as ultraviolet rays, visible rays, and radiations through a mask. In addition, you may further include the process of heating the photosensitive resin film after exposure if desired.

(Development process)
Subsequently, in the development step, a patterned resin film is obtained by removing the exposed portion 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 (TMAH). 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 curing process)
Next, in the heat curing step, for example, by using various heat diffusion furnaces, heating furnaces and curing furnaces, the obtained patterned resin film is preferably heat-treated at 150 to 450 ° C. It becomes a molecular pattern (pattern cured film). In the present invention, sufficient film characteristics can be obtained even if the heat treatment is performed at 350 ° C. or lower, preferably 150 to 300 ° C.

(Microwave curing)
The heat treatment is not limited to a thermal diffusion furnace or the like, and microwaves can also be used. When the microwave is irradiated in the form of pulses while changing the frequency, standing waves can be prevented and the substrate surface can be heated uniformly. In addition, when metal wiring is included as an electronic component as a substrate, it is possible to prevent the occurrence of electric discharge from the metal and to protect the electronic component from destruction by irradiating microwaves in pulses while changing the frequency. It is preferable at the point which can do.

  In the positive photosensitive resin composition of the present invention, the microwave frequency to be irradiated is in the range of 0.5 to 20 GHz, but is practically preferably in the range of 1 to 10 GHz, and more preferably in the range of 2 to 9 GHz. preferable.

  Although it is desirable to continuously change the frequency of the microwave to be irradiated, the irradiation is actually performed by changing the frequency stepwise. At that time, the shorter the time for irradiating a single-frequency microwave, the less likely it is that standing waves or metal discharges occur, and the time is preferably 1 millisecond or less, particularly preferably 100 microseconds or less.

  The output of the microwave to be irradiated varies depending on the size of the apparatus and the amount of the object to be heated, but is generally in the range of 10 to 2000 W, practically preferably 100 to 1000 W, more preferably 100 to 700 W, further preferably 100 to 700 W. 500 W is most preferred. If the output is 10 W or less, it is difficult to heat the object to be heated in a short time, and if it is 2000 W or more, a rapid temperature rise is likely to occur.

  In the positive photosensitive resin composition of the present invention, the microwave to be irradiated is preferably turned on / off in a pulsed manner. By irradiating the microwaves in a pulsed manner, the set heating temperature can be maintained, and damage to the polyimide thin film and the substrate can be avoided. Although the time for irradiating the pulsed microwave at one time varies depending on the conditions, it is approximately 10 seconds or less.

  In the positive photosensitive resin composition of the present invention, the time for heat curing is the time until the remaining solvent and volatile components are sufficiently scattered, but is approximately 5 hours or less in view of work efficiency. The atmosphere for the heat treatment can be selected from the air or an inert atmosphere such as nitrogen.

[Manufacturing process of semiconductor devices (electronic parts)]
Next, as an example of a pattern manufacturing method using the positive photosensitive resin composition according to the present invention, an example of a manufacturing process of a semiconductor device (electronic component) will be described with reference to the drawings. 1 to 5 are schematic cross-sectional views for explaining a manufacturing process of a semiconductor device having a multilayer wiring structure. 1 to 5, a semiconductor substrate 1 such as a Si substrate having a circuit element (not shown) is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and is exposed. A first conductor layer 3 is formed thereon. On this semiconductor substrate 1, an interlayer insulating film layer 4 such as a polyimide resin as an interlayer insulating film is formed by a spin coat method or the like (FIG. 1).

  Next, a chlorinated rubber-based or phenol novolac-based photosensitive resin layer 5 is formed on the interlayer insulating film layer 4 by a spin coating method, and a predetermined portion of the interlayer insulating film layer 4 is exposed by a known photolithography technique. A window 6A is provided as shown in FIG. The interlayer insulating film layer 4 exposed by the window 6A is selectively etched by a dry etching means using a gas such as oxygen or carbon tetrafluoride to open the window 6B. Next, the photosensitive resin layer 5 is completely removed using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B (FIG. 3).

  Further, the second conductor layer 7 is formed by using a known photolithography technique, and the electrical connection with the first conductor layer 3 is completely performed (FIG. 4). When a multilayer wiring structure having three or more layers is formed, each layer can be formed by repeating the above steps.

  Next, the surface protective film layer 8 is formed. In the illustrated example, the surface protective film layer 8 is coated with the photosensitive resin composition by a spin coat method, dried, and irradiated with light from a mask on which a pattern for forming a window 6C is formed at a predetermined portion. Then, development is performed with an aqueous alkali solution to form a pattern, which is then heated to form a heat resistant polymer film (FIG. 5). This heat-resistant polymer film as the surface protective film layer 8 protects the conductor layers 7 and 3 from external stress, α rays, etc., and the obtained semiconductor device is excellent in reliability. In the above example, not only the surface protective film layer 8 but also the interlayer insulating film layer 4 can be formed using the positive photosensitive resin composition of the present invention.

[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 components such as semiconductor devices and multilayer wiring boards. Specifically, the surface protective film, interlayer insulating film of semiconductor devices, and interlayers of multilayer wiring boards are used. It can be used for forming an insulating film or the like. The semiconductor device of 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. The electronic component according to the present invention includes a cured pattern film formed by the above-described method for producing a cured pattern film using the positive photosensitive resin composition of the present invention. Moreover, as an electronic component, a semiconductor device, a multilayer wiring board, various electronic devices, etc. are included.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples.

(Examples 1-12)
In Examples and Comparative Examples described later, the weight average molecular weight of the synthesized polymer was determined by gel permeation chromatography (GPC, apparatus manufactured by Hitachi, Ltd., column manufactured by Hitachi Chemical Co., Ltd. Gel Pack), It calculated | required by standard polystyrene conversion.

[Synthesis Example 1] Synthesis of polybenzoxazole precursor (component (a)) 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, N -After 90 g of methylpyrrolidone was charged and the flask was cooled 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 dicarboxylic 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 of bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP) (50 After stirring and dissolving, 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. Stirring was continued for a minute. The 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 carboxyl group-terminated polyhydroxyamide (hereinafter referred to as polymer I). The polymer I had a weight average molecular weight of 17,600 and a dispersity of 1.6 determined by GPC standard polystyrene conversion.

[Synthesis Example 2] Synthesis of polybenzoxazole precursor (component (a)) In a 0.5 liter flask equipped with a stirrer and a thermometer, 12.90 g (50 mmol) of 4,4'-diphenyl ether dicarboxylic acid, N -After charging 75 g of methylpyrrolidone and cooling the flask to 5 ° C., 19.9 g (100 mmol) of thionyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of 4,4′-diphenyl ether dicarboxylic acid chloride. Next, 105 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 22.0 g (60 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 5-norbornene were added. 2.28 g (20 mmol) of 2,3-dicarboxylic acid anhydride was added and dissolved by stirring. Then, 7.9 g (100 mmol) of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., 4,4 A solution of '-diphenyl ether dicarboxylic acid chloride was added dropwise over 30 minutes, and stirring was continued for 30 minutes. The obtained solution was poured into 3 liters of water, and the precipitate was collected, washed with pure water three times, and then dried under reduced pressure to obtain polyhydroxyamide having a double bond at the end (hereinafter referred to as Polymer II and To do). The polymer II had a weight average molecular weight of 22,800 and a dispersity of 1.8 determined by GPC standard polystyrene conversion.

[Synthesis Example 3] Synthesis of polybenzoxazole precursor (component (a)) In a 0.5 liter flask equipped with a stirrer and a thermometer, 12.90 g (50 mmol) of 4,4′-diphenyl ether dicarboxylic acid, N -After charging 75 g of methylpyrrolidone and cooling the flask to 5 ° C., 19.9 g (100 mmol) of thionyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of 4,4′-diphenyl ether dicarboxylic acid chloride. Next, 105 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 14.7 g (40 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane and m-amino were added. After 2.16 g (20 mmol) of phenol was added and dissolved by stirring, 7.9 g (100 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 to the solution. After dropwise addition in minutes, stirring was continued for 30 minutes. The obtained solution was poured into 3 liters of water, and the precipitate was collected, washed with pure water three times, and then dried under reduced pressure to obtain polyhydroxyamide having a phenol terminal (hereinafter referred to as polymer III). . The polymer III had a weight average molecular weight of 15,600 and a dispersity of 1.7 determined by GPC standard polystyrene conversion.

[Synthesis Example 4] Synthesis of polyimide precursor (component (a)) In a 0.2 liter flask equipped with a stirrer and a thermometer, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride ( (ODPA) 10 g (32 mmol) and isopropyl alcohol 3.87 g (65 mmol) were dissolved in 45 g of N-methylpyrrolidone, and after adding a catalytic amount of 1,8-diazabicycloundecene, heating was performed at 60 ° C. for 2 hours. Subsequently, the mixture was stirred at room temperature (25 ° C.) for 15 hours for esterification. Thereafter, 7.61 g (64 mmol) of thionyl chloride was added under ice cooling, and the mixture was returned to room temperature and reacted for 2 hours to obtain an acid chloride solution. This solution is referred to as acid chromate solution A.

  Next, in a 0.5 liter flask equipped with a stirrer and a thermometer, 40 g of N-methylpyrrolidone was charged, 10.25 g (28 mmol) of 6FAP was added, dissolved by stirring, and then 5.06 g (64 mmol) of pyridine. ) Was added, and while maintaining the temperature at 0 to 5 ° C., the previously prepared acid chromatography solution A was added dropwise over 30 minutes, and then stirring was continued for 30 minutes. The reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a carboxylate-terminated polyamic acid ester (hereinafter referred to as polymer IV). Polymer IV had a weight average molecular weight of 19,400 and a dispersity of 2.2.

[Synthesis Example 5] Synthesis of polyimide precursor (component (a)) In a 0.2 liter flask equipped with a stirrer and a thermometer, 6.54 g (30 mmol) of pyromellitic dianhydride (PMDA) and methyl were added. 1.92 g (60 mmol) of alcohol was dissolved in 20 g of N-methylpyrrolidone, and a catalytic amount of 1,8-diazabicycloundecene was added, followed by heating at 60 ° C. for 2 hours, and subsequently at room temperature ( The mixture was stirred at 25 ° C. for 15 hours for esterification. Thereafter, 7.25 g (61 mmol) of thionyl chloride was added under ice cooling, and the mixture was returned to room temperature and reacted for 2 hours to obtain an acid chloride solution. This solution is referred to as acid chloride solution B.

  Next, in a 0.5 liter flask equipped with a stirrer and a thermometer, 12.3 g of N-methylpyrrolidone was charged, and 5.73 g (27 mmol) of 2,2′-dimethylbenzidine (DMAP) was added and dissolved by stirring. Then, 4.82 g (61 mmol) of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., the previously prepared acid chromatography solution B was added dropwise over 30 minutes, and then stirring was continued for 30 minutes. The reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a carboxylate terminal polyamic acid ester. (Hereinafter referred to as polymer V). Polymer V had a weight average molecular weight of 32,800 and a dispersity of 2.5.

[Synthesis Example 6] Synthesis of polyimide precursor (component (a)) In a 0.5 liter flask equipped with a stirrer and a thermometer, 40 g of N-methylpyrrolidone was charged, and 7.64 g (36 mmol) of DMAP and 5 -After adding 1.31 g (8 mmol) of norbornene-2,3-dicarboxylic acid anhydride and stirring and dissolving, 5.06 g (64 mmol) of pyridine is added and the temperature is kept at 0 to 5 ° C. The acid chromate solution B (corresponding to PMDA 32 mmol) prepared in the same manner as above was added dropwise over 30 minutes, and stirring was continued for 30 minutes. The reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamic acid ester having a double bond at the end (hereinafter referred to as polymer VI). The weight average molecular weight of polymer VI was 31,400, and the degree of dispersion was 2.1.

[Synthesis Example 7] Synthesis of polyimide precursor (component (a)) In a 0.5 liter flask equipped with a stirrer and a thermometer, 40 g of N-methylpyrrolidone was charged and 2,2′-bis (trifluoromethyl). ) 12.81 g (40 mmol) of benzidine (TFDB) was added and dissolved by stirring. Then, 6.01 g (76 mmol) of pyridine was added and the temperature was kept at 0 to 5 ° C. B (equivalent to PMDA 38 mmol) was added dropwise over 30 minutes, and stirring was continued for 30 minutes. This reaction solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamic acid ester having an amino group at the terminal (hereinafter referred to as polymer VII). The weight average molecular weight of polymer VII was 29,100, and the degree of dispersion was 1.7.

[Synthesis Example 8] Synthesis of polyimide precursor (component (a)) In a 0.5 liter flask equipped with a stirrer and a thermometer, 40 g of N-methylpyrrolidone was charged, and 11.53 g (36 mmol) of TFDB, m- After adding 0.43 g (4 mmol) of aminophenol and dissolving by stirring, 6.01 g (76 mmol) of pyridine was added and the temperature was kept at 0 to 5 ° C., while the acid chromate solution B ( PMDA 38 mmol) was added dropwise over 30 minutes, and stirring was continued for 30 minutes. The reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamic acid ester having a phenol terminal (hereinafter referred to as polymer VIII). Polymer VIII had a weight average molecular weight of 31,100 and a dispersity of 1.8.

[Photosensitive evaluation]
Table 1 shows the components (a) to (c) blended. As a notation, the polymer selected as the component (a) is shown in units of parts by weight so that the total weight of the component (a) is 100 parts by weight. Moreover, (b) component, (c) component, and the organic solvent were shown as a weight part with respect to 100 weight part of (a) component. As the organic solvent, N-methylpyrrolidone (NMP) was used. In Table 1, the amount added in () is shown in parts by weight with respect to 100 parts by weight of the total amount of polymer.

  In the above (Table 1), B1 and B2 used as the component (b) and C1 to C7 used as the component (c) are compounds shown in the following [Chemical 9] and [Chemical 10].

The solution is spin-coated on a silicon wafer to form a coating film having a dry film thickness of 7 to 12 μm, and then an i-line exposure of 100 to 1000 mJ / cm ² using an ultrahigh pressure mercury lamp through an interference filter. went. After exposure, the film is heated at 120 ° C. for 3 minutes, developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) until the exposed silicon wafer is exposed, and then rinsed with water to maintain the remaining film ratio (development) The minimum exposure amount (sensitivity) and the resolution required for pattern formation with which the ratio of the film thickness before and after) was 80% or more were determined. The results are summarized in the following (Table 2).

  Subsequently, the 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 150 ° C. for 30 minutes in a nitrogen atmosphere, and further heated at 320 ° C. for 1 hour to obtain a cured film. Next, the obtained film is immersed in a hydrofluoric acid aqueous solution together with the silicon substrate, the cured film is peeled off from the substrate, washed with water and dried, and then the glass transition point (Tg), thermal expansion coefficient (CTE), elongation at break, elasticity The rate (measured with a tensile tester) was measured. These results are shown below (Table 3).

(Comparative Examples 1-5)
The prescribed amounts shown below (Table 4) were blended, and the cured film thus obtained was evaluated in the same manner as in the previous examples.

  In the above (Table 4), the amount in () indicates the amount added relative to 100 parts by weight of the total amount of polymer in parts by weight. In Table 4, B1 and B2 used as the component (b), and C1 and C2 used as the component (c) are compounds having the structures shown in the above [Chemical 9] and [Chemical 10].

  Next, in the same manner as in the examples, the solution is spin-coated on a silicon wafer, and after exposure and development, rinsed with water to form a pattern with a remaining film ratio (ratio of film thickness before and after development) of 80% or more. The required minimum exposure (sensitivity) and resolution were determined. The results are summarized in the following (Table 5).

  In the case of Comparative Example 2, the component (b) was not added, no photoreaction occurred in the exposed area, and no pattern was formed. In Comparative Examples 4 and 5, the component (b) reacted in the exposed area, but the exposed area did not dissolve because the component (a) used did not dissolve in the alkaline developer. The pattern was not formed.

  Moreover, the cured film characteristic of Comparative Examples 1-5 was measured like the Example. The results are shown in Table 6.

  In Comparative Examples 1 and 3, the photosensitive characteristics were inferior to those in Examples, but the cured film characteristics were greatly inferior to those in Examples. On the contrary, Comparative Examples 2, 4, and 5 could not form a pattern, but the cured film characteristics were good. As described above, in the comparative example, it was not possible to achieve both photosensitive characteristics and cured film characteristics.

  As described above, the positive photosensitive resin composition according to the present invention enables pattern formation with excellent sensitivity and resolution. In addition, the positive photosensitive resin composition of the present invention is excellent in pattern formation, and the heat-cured film is excellent in heat resistance and can have arbitrary characteristics such as low thermal expansion, high elasticity, and low elasticity. . Moreover, according to the method for producing a cured pattern film of the present invention, a cured pattern film having a good shape and excellent sensitivity, resolution, and heat resistance can be obtained by using the positive photosensitive resin composition. Furthermore, the electronic component of the present invention has high reliability by having a pattern cured film having a good shape and characteristics. Therefore, the present invention is useful for electronic components such as electronic devices.

It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure in embodiment of this invention. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure in embodiment of this invention. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure in embodiment of this invention. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure in embodiment of this invention. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure in embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Semiconductor substrate 2 Protective film 3 1st conductor layer 4 Interlayer insulation film layer 5 Photosensitive resin layer 6A, 6B, 6C, 6D Window 7 2nd conductor layer 8 Surface protective film layer

Claims (10)

  A positive photosensitive material comprising: (a) a polymer component comprising two or more different heat-resistant polymers having reactive end groups; and (b) a compound that generates an acid upon irradiation with actinic rays. Resin composition.   (A) a heat-resistant polymer in which at least one of the polymer components is selected from the group consisting of polyimide, polyoxazole, polyamideimide, polyamide, polyamic acid, polyamic acid ester, polyhydroxyamide, and copolymers thereof The positive photosensitive resin composition according to claim 1, wherein the positive photosensitive resin composition is a compound.   The positive photosensitive resin composition according to claim 1, wherein at least one of the polymer components (a) is soluble in an alkaline aqueous solution.   The component (a) contains a compound capable of crosslinking with an end group of at least one polymer of the (a) polymer component by heat in addition to the (a) polymer component and the (b) component. The positive photosensitive resin composition of any one of 1-3.   (A) at least one of the polymer components contains a functional group or a bond selected from the group consisting of primary or secondary alcohols, carboxyl groups, amino groups, thiols, phenols and aromatic rings, and the component (c) Is a functional group or bond selected from the group consisting of methylol, alkoxyalkyl groups, tertiary alcohols, cycloalkyl groups, olefins, triple bonds, halogenated alkyls, epoxy groups and other cyclic ethers, ester bonds, carbonates and isocyanates The positive photosensitive resin composition according to claim 1, comprising:   (A) At least one of the polymer components comprises a methyl ether, an alkoxyalkyl group, a tertiary alcohol, a cycloalkyl group, an olefin, a triple bond, an alkyl halide, a cyclic ether such as an epoxy group, an ester bond, a carbonate and an isocyanate. A functional group or bond selected from the group, and wherein the component (c) is selected from the group consisting of primary or secondary alcohols, carboxyl groups, amino groups, thiols, phenols and aromatic rings The positive photosensitive resin composition according to claim 1, comprising:   The positive photosensitive resin composition according to claim 1, wherein the component (b) is an o-quinonediazide compound.   The component (b) contains 0.01 to 50 parts by weight of the component (b) and 0.1 to 50 parts by weight of the component (c) with respect to 100 parts by weight of the total amount of the polymer components. Item 8. The positive photosensitive resin composition according to Item 7. A photosensitive resin film forming step in which the positive photosensitive resin composition according to any one of claims 1 to 8 is applied on a support substrate and dried to form a photosensitive resin film;
An exposure step of exposing the photosensitive resin film;
A development step of developing the exposed photosensitive resin film using an aqueous alkaline solution to obtain a patterned resin film;
And a heat-curing step of obtaining a patterned cured film by heat-treating the patterned resin film.   An electronic component having an electronic device having a patterned cured film layer obtained by the method for producing a patterned cured film according to claim 9, wherein the patterned cured film layer is an interlayer insulating film in the electronic device. An electronic component provided as a layer or / and a surface protective film layer.

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