JP4775077B2 - Positive photosensitive polyamideimide resin composition, pattern manufacturing method, and electronic component - Google Patents

Description

  The present invention relates to a positive photosensitive polyamideimide resin composition, a method for producing a pattern, and an electronic component, and in particular, it can be developed with an alkaline aqueous solution, and is excellent in sensitivity, resolution, adhesion during development, and heat resistance. The present invention relates to a positive photosensitive polyamideimide resin composition capable of obtaining a pattern having a simple shape, a method for producing a pattern, and an electronic component.

  Polyimide resins have excellent heat resistance, electrical characteristics, mechanical characteristics, etc., and are used for surface protection films and interlayer insulation films of semiconductor elements. This polyimide resin film is formed by thinning a polyimide precursor (polyamic acid) solution (so-called varnish) obtained by reacting tetracarboxylic dianhydride and diamine with spin coating, etc., and thermally dehydrating and ring-closing (so-called curing) (For example, refer nonpatent literature 1).

  In recent years, semiconductor devices have been highly integrated and increased in size, and there has been a demand for thinner and smaller sealing resin packages, and surface mounting methods such as LOC (lead-on-chip) and solder reflow have been adopted. Therefore, a polyimide resin excellent in mechanical properties, heat resistance and the like has been required more than ever.

  Recently, a photosensitive polyimide having a photosensitive property imparted to the polyimide resin itself has been used. However, if this is used, the pattern creation process can be simplified, and the complicated manufacturing process can be shortened (for example, Patent Documents 1 to 3). In recent years, in order to compensate for the lack of sensitivity in resists for semiconductor microfabrication, chemically amplified resists that combine light irradiation and thermal reaction have been proposed (Non-Patent Document 2), and chemically amplified photosensitive polyimides have also been studied. (For example, see Patent Document 4).

  As described above, the polyimide resin film is formed by curing the precursor film, but volume shrinkage due to dehydration (imidization) occurs at the time of curing, resulting in a loss of film thickness and a decrease in dimensional accuracy. Recently, a low-temperature process has been desired, and a polyimide that can perform dehydration and ring closure at a low temperature and has properties that are comparable to those obtained by dehydration and ring closure at high temperatures is obtained. However, when the polyimide precursor is cured at a reduced temperature, imidization is incomplete, so the cured film is brittle and the physical properties decrease.

In contrast to the polyimide (precursor) resin described above, the ring-closed polyamideimide resin has no volume shrinkage due to dehydration during curing, and has already been imidized, and thus has a possibility of being compatible with a low temperature process.
As a photosensitive polyamideimide resin obtained by imparting photosensitive properties to a polyamideimide resin, a solvent development negative type having a photopolymerizable unsaturated bond in the molecule is known (for example, see Patent Documents 5 and 6). Furthermore, a positive photosensitive polyamideimide resin composition containing an orthonaphthoquinonediazide sulfonic acid compound is also known (see, for example, Patent Documents 7 to 9).

Japan Polyimide Study Group "Latest Polyimides-Fundamentals and Applications" (2002) "Latest Resist Material Handbook-Material Properties / Design and Control / Troubleshooting-" (2005), published by Information Organization Co., Ltd. Japanese Patent Laid-Open No. 49-11541 JP 59-108031 A JP 59-219330 A JP 2001-166484 A JP-A-10-292019 JP 2003-280196 A Japanese Patent No. 2524240 Japanese Patent No. 2524241 Japanese Patent No. 2902761

  The exposure wavelength of the photosensitive heat-resistant resin has shifted from the conventional g and h lines to the i line on the shorter wavelength side due to high integration of semiconductors, low cost, and reduction of environmental load. In addition, as with semiconductor resist materials, the conventional solvent development is shifting to a positive type compatible with alkali (specifically, tetramethylammonium hydroxide (TMAH)) aqueous solution development.

  However, it is excellent in sensitivity, resolution, adhesion at the time of development, and heat resistance, a pattern having a good shape can be obtained, and a positive photosensitive polyamideimide resin composition that can be developed with an alkaline aqueous solution in response to recent demands There is a problem that the current situation is demanded.

The present invention has been made in order to solve the above-described conventional problems. With respect to a photosensitive polyamide-imide resin, it can be developed with an aqueous alkali (TMAH) solution and has a high sensitivity. A resin composition is provided.
In addition, the present invention uses the positive photosensitive polyamideimide resin composition using a polyamideimide in which an alkali-soluble group is protected with a protecting group that can be removed in the presence of an acid. The manufacturing method of the pattern which is excellent in the adhesiveness of this, and was excellent in heat resistance and in which the pattern of a favorable shape is obtained is provided.
In addition, the present invention has a pattern with a good shape and characteristics, has a small volume shrinkage at the time of curing, has high dimensional stability, and can be cured by a low temperature process, thereby avoiding damage to the device and being reliable. High-performance electronic components are provided with high yield.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive research. As a result, a photosensitive resin comprising an aqueous alkali-soluble soluble polyamideimide in which an alkali-soluble group is protected with a protecting group that can be removed in the presence of an acid. It has been found that the composition can be developed with an aqueous alkali (TMAH) solution and is excellent in sensitivity, resolution, and adhesion during development. Further, the present inventors have found that the film shrinkage at the time of curing is small and that sufficient film properties are exhibited even when cured at a low temperature of 200 ° C. or less, and the present invention has been completed.

  That is, the positive photosensitive polyamideimide resin composition of the present invention has a group (A) bonded to an aromatic ring and represented by -OR in the molecule (provided that R is decomposed by the action of an acid and converted to a hydrogen atom. And a polyamideimide having a group selected from the group consisting of a monovalent acetal or ketal group, an alkoxyalkyl group, an alkylsilyl group, an alkoxycarbonyl group and an alkyl group), and (B) radiation. It contains a compound that generates an acid upon irradiation, and (C) a solvent.

（式中、ｍは１以上の正数である。また、式中、Ｕは（２＋ｍ）価の有機基を示し、Ｖは３価の有機基を示し、Ｗは活性水素を有さない２価の有機基を示す。また、Ｒは酸の作用で分解し水素原子に変換し得る、一価のアセタールもしくはケタールを構成する基、アルコキシアルキル基、アルキルシリル基、アルコキシカルボニル基及びアルキル基からなる群から選択される基を示す。） In the positive photosensitive polyamideimide resin composition of the present invention, the component (A) is a polyamideimide having a repeating unit represented by the following general formula (I).

(In the formula, m is a positive number of 1 or more. In the formula, U represents a (2 + m) -valent organic group, V represents a trivalent organic group, and W has no active hydrogen. 2 R represents an organic group having a monovalent acetal or ketal, an alkoxyalkyl group, an alkylsilyl group, an alkoxycarbonyl group, and an alkyl group that can be decomposed by the action of an acid and converted into a hydrogen atom. A group selected from the group consisting of:

（式中、ｍ’は１以上の正数であり、ｎ’は１〜１，０００の正数である。また、式中、Ｕ’は（２＋ｍ）価の有機基を示し、Ｇは４価の有機基を示す。また、Ｒは酸の作用で分解し水素原子に変換し得る、一価のアセタールもしくはケタールを構成する基、アルコキシアルキル基、アルキルシリル基、アルコキシカルボニル基及びアルキル基からなる群から選択される基を示す。） The positive photosensitive polyamideimide resin composition of the present invention is characterized in that U in the general formula (I) is an organic group represented by the general formula (II).

(In the formula, m ′ is a positive number of 1 or more, n ′ is a positive number of 1 to 1,000, and U ′ represents a (2 + m) -valent organic group, and G is 4) R represents an organic group having a monovalent acetal or ketal, an alkoxyalkyl group, an alkylsilyl group, an alkoxycarbonyl group, and an alkyl group that can be decomposed by the action of an acid and converted into a hydrogen atom. A group selected from the group consisting of:

  In the positive photosensitive polyamideimide resin composition of the present invention, V in the general formula (I) is an organic group having a substituted or unsubstituted cyclic structure.

  Moreover, in the positive photosensitive polyamideimide resin composition of the present invention, the positive photosensitive polyamideimide resin composition has the above-mentioned (B) component 0. It is characterized by blending 01 to 50 parts by weight.

  In the positive photosensitive polyamideimide resin composition of the present invention, the component (B) is an aromatic N-oxyimide sulfonate, onium salt or oxime ester.

  In the positive photosensitive polyamideimide resin composition of the present invention, the positive photosensitive polyamideimide resin composition can be further converted into a carboxylic acid or a phenolic hydroxyl group by (D) acid catalysis. It is characterized by including the compound which has these.

  In the positive photosensitive polyamideimide resin composition of the present invention, the component (D) is a group represented by -COOQ in the molecule (where Q is decomposed by the action of an acid and converted to a hydrogen atom. It is a compound having a monovalent organic group capable of being).

  Moreover, in the positive photosensitive polyamideimide resin composition of the present invention, the positive photosensitive polyamideimide resin composition contains 1 component (D) with respect to 100 parts by weight of the component (A). It is characterized by containing ~ 100 parts by weight.

  In the pattern production method of the present invention, the positive photosensitive polyamideimide resin composition is coated on a support substrate and dried, and the photosensitive resin film obtained by the drying step is exposed. And a step of developing the exposed photosensitive resin film using an alkaline aqueous solution, and a step of heat-treating the photosensitive resin film after the development.

  In the pattern manufacturing method of the present invention, a heating step is further included after the exposure step.

  In the pattern manufacturing method of the present invention, the heating temperature is 200 ° C. or less in the step of heat-treating the photosensitive resin film after development.

  The electronic component of the present invention is characterized by having a pattern layer obtained by the pattern manufacturing method as an interlayer insulating film layer or a surface protective film layer.

  The positive photosensitive polyamideimide resin composition of the present invention is low in cost since only carbon dioxide is produced as a by-product when producing a polyamideimide having an alkali aqueous solution-soluble group, and purification is easy or unnecessary. Moreover, since the positive photosensitive polyamideimide resin composition of the present invention is a chemically amplified type, the resulting pattern is excellent in sensitivity. Furthermore, since the positive photosensitive polyamideimide resin composition of the present invention can be developed with an aqueous TMAH solution, it is low in cost and has a low load on the global environment.

  In addition, according to the method for producing a pattern of the present invention, by using the positive photosensitive polyamideimide resin composition, even in a low temperature curing process, the sensitivity, resolution and adhesiveness are excellent, and heat resistance A pattern having a good shape and excellent physical properties can be obtained. Moreover, according to the pattern manufacturing method of the present invention, the positive photosensitive polyamide-imide resin composition has a small volume shrinkage at the time of curing, so that a pattern with excellent dimensional stability can be obtained.

  In addition, the electronic component of the present invention has a good shape, adhesion and heat resistance, and can be cured by a low-temperature process. is there. In addition, since the device is less damaged, a high yield can be obtained. Furthermore, since the glass transition temperature of the cured film obtained by curing the film of the positive photosensitive resin composition is high, it can withstand a heating process such as sealing or solder reflow when mounting an electronic component having the cured film. There is an effect.

  Hereinafter, an embodiment of a positive photosensitive polyamideimide resin composition, a pattern production method, and an electronic component according to the present invention will be described in detail with reference to the drawings. In addition, this invention is not limited by the following embodiment.

[Positive photosensitive polyamide-imide resin composition]
First, the positive photosensitive polyamideimide resin composition according to the present invention will be described.
The positive photosensitive polyamide-imide resin composition of the present invention is a group (A) bonded to an aromatic ring and represented by -OR in the molecule (provided that R is decomposed by the action of an acid and can be converted to a hydrogen atom. A group comprising a monovalent acetal or ketal, an alkoxyalkyl group, an alkylsilyl group, an alkoxycarbonyl group and a group selected from the group consisting of an alkyl group.) And (B) by radiation irradiation A positive photosensitive polyamide-imide resin composition comprising an acid-generating compound and (C) a solvent.
Hereinafter, each component contained in the positive photosensitive polyamideimide resin composition will be described. The (A) polyamideimide, (B) a compound that generates an acid upon irradiation with radiation, and (C) a solvent are simply referred to as a component (A), a component (B), and a component (C), respectively, as necessary.

[(A) Polyamideimide]
The component (A) of the positive photosensitive polyamideimide resin composition is polyamideimide, and is a group bonded to an aromatic ring and represented by -OR in the molecule (provided that R is decomposed by the action of an acid to form a hydrogen atom And a group selected from a group constituting a monovalent acetal or ketal, an alkoxyalkyl group, an alkylsilyl group, an alkoxycarbonyl group, an alkyl group and the like. When the above R is decomposed by the action of an acid and converted to a hydrogen atom, a phenolic hydroxyl group is generated, so that an appropriate alkali solubility is imparted to the composition of the present invention.

  In the present invention, the group bonded to the aromatic ring and represented by -OR in the molecule may be present via the main chain or side chain in the polyamideimide, and the number thereof is a structural unit of polyamideimide. 1 or more, preferably 1 to 5,000, more preferably 1 to 1,000.

（式中、Ｒ'、Ｒ’’及びＲ’’’は各々独立に炭素数５以下のアルキル基であり、Ｘは炭素数２以上（好ましくは２０以下）の２価のアルキレン基（側鎖を有していてもよい）である。） In the present invention, R in the molecule bonded to an aromatic ring and represented by -OR is a group constituting a monovalent acetal or ketal which can be decomposed by the action of an acid and converted into a hydrogen atom, alkoxyalkyl A group (so-called protecting group) represented by a group, an alkylsilyl group, an alkoxycarbonyl group, an alkyl group or the like. Examples of the group constituting a monovalent acetal or ketal that can be decomposed by the action of an acid and converted into a hydrogen atom, or an alkoxyalkyl group include those having a structure represented by the following general formula (III).

Wherein R ′, R ″ and R ′ ″ are each independently an alkyl group having 5 or less carbon atoms, and X is a divalent alkylene group having 2 or more (preferably 20 or less) carbon atoms (side chain) May be included).)

  Specifically, tetrahydropyranyl group, tetrahydrofuranyl group, alkyl substituted tetrahydropyranyl group, alkyl substituted tetrahydrofuranyl group, alkoxy substituted tetrahydropyranyl group, alkoxy substituted tetrahydrofuranyl group, methoxymethyl group, ethoxymethyl group, isopropoxy A methyl group, a t-butoxymethyl group, a benzyloxymethyl group, a methoxyethoxymethyl group, a 1-ethoxyethyl group, and the like are exemplified as typical examples, but are not limited thereto. Most preferred groups are a tetrahydropyranyl group, an ethoxymethyl group, and a 1-ethoxyethyl group.

  The monovalent alkylsilyl group that can be decomposed by the action of an acid and converted into a hydrogen atom is not particularly limited, but preferably has 1 to 20 carbon atoms. Specifically, a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a t-butyldiphenylsilyl group, a triisopropylsilyl group, and the like are shown as typical examples, but are not limited thereto. Most preferred groups are a trimethylsilyl group and a t-butyldimethylsilyl group.

  The monovalent alkoxycarbonyl group that can be decomposed by the action of an acid and converted into a hydrogen atom is not particularly limited, but a preferable carbon number is 2 to 13. Specific examples include a methoxycarbonyl group, a t-butoxycarbonyl group, an adamantyloxycarbonyl group, and a vinyloxycarbonyl group, but are not limited thereto. The most preferred group is t-butoxycarbonyl group.

The monovalent alkyl group that can be decomposed by the action of an acid and converted into a hydrogen atom is not particularly limited, but a preferable carbon number is 1 to 12. Specific examples include a t-butyl group, a cyclopropylmethyl group, a cyclohexyl group, an allyl group, and a p-methoxybenzyl group, but are not limited thereto.
As a protecting group other than the above (a group that can be decomposed by the action of an acid and converted into a hydrogen atom), a methylthiomethyl group, a sulfonate ester, a phosphate ester, or the like can also be used.

  The polyamideimide as the component (A) in the present invention is decomposed by the action of the acid described above, and is a phenolic hydroxyl group (bonded to an aromatic ring and represented by —OH) with a functional group (protecting group) that can be converted to a hydrogen atom. There is no particular limitation as long as it is a polyamideimide protecting the group). For example, what protected the phenolic hydroxyl group of the polyamideimide which has the phenolic hydroxyl group described in patent 2524240, 2524241, 2902761 and Unexamined-Japanese-Patent No. 2002-88154 by the said protective group is this invention. It can be used as a polyamideimide.

（式中、ｍは１以上の正数である。また、式中、Ｕは（２＋ｍ）価の有機基を示し、Ｖは３価の有機基を示し、Ｗは活性水素を有さない２価の有機基を示す。また、Ｒは酸の作用で分解し水素原子に変換し得る、一価のアセタールもしくはケタールを構成する基、アルコキシアルキル基、アルキルシリル基、アルコキシカルボニル基、アルキル基等を示す。） Moreover, it is preferable that the polyamideimide which is (A) component in this invention is a polyamideimide which has a repeating unit shown by the following general formula (I) from the ease of a synthesis | combination.

(In the formula, m is a positive number of 1 or more. In the formula, U represents a (2 + m) -valent organic group, V represents a trivalent organic group, and W has no active hydrogen. 2 R represents a monovalent acetal or ketal, an alkoxyalkyl group, an alkylsilyl group, an alkoxycarbonyl group, an alkyl group, etc. that can be decomposed by the action of an acid and converted into a hydrogen atom. Is shown.)

  Here, the number m of the protected phenolic hydroxyl groups (-OR) per repeating unit structure is a positive number of 1 or more, preferably 1 to 5,000 in consideration of the balance of solubility, 1,000 is more preferable. In addition, when the number of repeating units represented by the general formula (I) is n (degree of polymerization n), the number is not particularly limited, but considering the balance of solubility and heat resistance, 2 to A positive number of 10,000 is preferable, and 3 to 5,000 is more preferable.

  In the general formula (I), R is a functional group (protecting group) that can be decomposed by the action of an acid and converted into a hydrogen atom, and the details thereof are the same as those described above.

  In the general formula (I), U is a (2 + m) valent organic group, and the m valence is bonded to the oxygen atom of the OR group and the divalent is bonded to the nitrogen atom of the imide group. Specific examples of such U include the following residues of diamine (a1) having a phenolic hydroxyl group. That is, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 2,2-bis (3-amino-4-hydroxyphenyl) propane, , 2-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-hexafluoropropane, 9,9-bis (3-amino-4-hydroxyphenyl) fluorene, 9,9-bis {4- (3-amino-4-hydroxyphenoxy) fe Fluorene, 1,3-bis (3-amino-4-hydroxyphenyl) adamantane, 1,3-bis {4- (3-amino-4-hydroxyphenoxy) phenyl} adamantane, 2,2-bis (3 -Amino-4-hydroxyphenyl) adamantane, 2,2-bis {4- (3-amino-4-hydroxyphenoxy) phenyl} adamantane, 2- (3-hydroxy-4-aminophenyl) -2- (3- Amino-4-droxyphenyl) hexafluoropropane, 3,3′-dihydroxy-4,4′-diaminobenzophenone, 3,3′-diamino-4,4′-dihydroxybenzophenone, 3,3′-dihydroxy-4 , 4′-diaminodiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 3,3′- Hydroxy-4,4′-diaminodiphenylmethane, 2,6-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3-hydroxy-4,4′-diaminobiphenyl, 4-hydroxy-3,3 '-Diaminobiphenyl, 2- (3-amino-4-hydroxyphenyl) -2- (3-aminophenyl) hexafluoropropane, 3-hydroxy-4,4'-diaminodiphenylsulfone, 3-hydroxy-4,4 Examples include, but are not limited to, '-diaminodiphenyl ether, 3-hydroxy-4,4'-diaminodiphenylmethane. These structures can be used alone or in combination of two or more.

  Furthermore, from the viewpoint of solubility, U is more preferably the following general formula (II). As a specific example of the following general formula (II), the residue of the condensate (imidized diamine oligomer having a phenolic hydroxyl group) of the above diamine having a phenolic hydroxyl group (a1) and tetracarboxylic dianhydride is used. Corresponding structure.

（式中、ｍ’は１以上の正数であり、ｎ’は１〜１０００の正数である。また、式中、Ｕ’は（２＋ｍ）価の有機基を示し、Ｇは４価の有機基を示す。また、Ｒは酸の作用で分解し水素原子に変換し得る、一価のアセタールもしくはケタールを構成する基、アルコキシアルキル基、アルキルシリル基、アルコキシカルボニル基、アルキル基等を示す。）

(In the formula, m ′ is a positive number of 1 or more, n ′ is a positive number of 1 to 1000, and U ′ represents a (2 + m) -valent organic group, and G is a tetravalent group. R represents an organic group, and R represents a monovalent acetal or ketal-constituting group, alkoxyalkyl group, alkylsilyl group, alkoxycarbonyl group, alkyl group, etc., which can be decomposed by the action of an acid and converted into a hydrogen atom. .)

  Examples of tetracarboxylic dianhydrides include 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, pyromellitic anhydride, oxydiphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetra Carboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid Dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, diphthalic acid sulfide dianhydride, m-terphenyl-3, 3 ', 4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3', 4,4'-tetracarboxylic dianhydride, 1,1,1,3,3,3-hexa Fluoro-2,2-bis (3 4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis [4 ′-(3,4-dicarboxyphenoxy) phenyl] Propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis [4 ′-(3,4-dicarboxyphenoxy) phenyl] propane dianhydride, sulfonyldiphthalic acid Anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, cyclobutanetetracarboxylic dianhydride, 2,3,5,6-tetracarboxynorbornane dianhydride, bis (3,4-dica Ruboxycyclohexyl) ether, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 9,9-bis {4- (3,4-dicarboxyphenoxy) phenyl} fluorene dianhydride, 1 , 3-bis (3,4-dicarboxyphenyl) adamantane dianhydride, 1,3-bis {4- (3,4-dicarboxyphenoxy) phenyl} adamantane dianhydride, 2,2-bis (3 4-dicarboxyphenyl) adamantane dianhydride, 2,2-bis {4- (3,4-dicarboxyphenoxy) phenyl} adamantane dianhydride, and the like are exemplified, but not limited thereto. These compounds can be used alone or in combination of two or more.

  The imidized diamine oligomer having a phenolic hydroxyl group is an organic solvent that uses the diamine (a1) having the phenolic hydroxyl group and the tetracarboxylic dianhydride as necessary (for example, N-methyl-2-pyrrolidone). , N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide, γ-butyrolactone, toluene, benzene, etc.). The imidization is performed by, for example, a method of heating and refluxing using toluene or xylene, and the reaction temperature is preferably 30 to 300 ° C, more preferably 50 to 250 ° C. Further, a method of heating in the presence of a base catalyst such as pyridine is also used, and the reaction temperature is preferably -20 to 200 ° C, more preferably 0 to 150 ° C. The reaction time is approximately 10 minutes to 10 hours, and the atmosphere may be either air or an inert gas atmosphere, and can be performed in a pressurized or reduced pressure atmosphere in addition to atmospheric pressure. Here, it is preferable to use a method in which toluene or xylene is used under heating and reflux, because the imidized diamine oligomer having a phenolic hydroxyl group can be used for the subsequent reaction without purification.

  When synthesizing the imidized diamine oligomer having the phenolic hydroxyl group, the blending ratio of the diamine having the phenolic hydroxyl group (a1) and the tetracarboxylic dianhydride is about 4 mol per 1 mol of the diamine having a phenolic hydroxyl group. Carboxylic dianhydride is preferably 0.01 mol to 0.99 mol, more preferably 0.1 mol to 0.9 mol, and even more preferably 0.2 mol to 0.8 mol. If the tetracarboxylic dianhydride is less than 0.01 mol or exceeds 0.99 mol, it is difficult to adjust the dissolution rate.

  In the general formula (II), m ′ is a positive number of 1 or more, and is generally 1 to 1,000. N ′ is preferably a positive number from 1 to 1000. In the formula, U ′ represents a (2 + m) -valent organic group, and the structure of U in the general formula (I) can be preferably used. In general formula (II), R is the same as described in general formula (I). Moreover, G can mention the residue of the tetracarboxylic dianhydride mentioned previously suitably.

  In the general formula (I), V is a trivalent organic group, divalent forms an imide ring, and monovalent forms an amide bond. Specific examples of such V include the following residues of tricarboxylic acid monoanhydride (a2). Among these, an aromatic cyclic structure is more preferable from the viewpoint of heat resistance and the like, and an aliphatic cyclic structure is further preferable from the viewpoint of solubility in an alkaline aqueous solution, i-line transparency, heat resistance, and the like.

  Such tricarboxylic acid monoanhydrides include trimellitic anhydride (1,2,4-tricarboxybenzene-1,2 anhydride), hemimellitic anhydride (1,2,3-tricarboxybenzene-1, 2 anhydride), 2,3,5-tricarboxynaphthalene-2,3-anhydride, 4- (4-carboxyphenoxy) phthalic anhydride, 1,2,4-carboxycyclohexane-1,2 anhydride, 1,2,3-tricarboxycyclopropane-1,2 anhydride, 1,2,3-tricarboxycyclobutane-1,2 anhydride, aconitic acid anhydride, and the like, but are not limited thereto. Absent. These compounds can be used alone or in combination of two or more. Among these tricarboxylic acid monoanhydrides, from the viewpoint of heat resistance and the like, trimellitic acid anhydride, hemimellitic acid anhydride, 2,3,5-tricarboxynaphthalene-2,3-anhydride, 4- (4-carboxyphenoxy) ) Phthalic anhydride, 1,2,4-carboxycyclohexane-1,2 anhydride, 1,2,3-tricarboxycyclopropane-1,2 anhydride, 1,2,3-tricarboxycyclobutane-1, Cyclic tricarboxylic acid monoanhydrides such as dianhydrides are preferred. Furthermore, 1,2,4-carboxycyclohexane-1,2 anhydride, 1,2,3-tricarboxycyclopropane-1,2 anhydride from the viewpoint of solubility in alkaline aqueous solution, i-line transparency, heat resistance and the like Alicyclic tricarboxylic acid monoanhydrides such as 1,2,3-tricarboxycyclobutane-1,2 anhydride are preferred.

  In the above general formula (I), W is a divalent organic group having no active hydrogen, and forms an amide bond. Specifically as such W, the residue of the diisocyanate (a3) shown below can be mentioned suitably. In addition, when active hydrogen exists in W, since the diisocyanate group of a substrate reacts, it is inconvenient.

  As such diisocyanates, 1,3-bis (1-isocyanato-1-methylethyl) benzene, 1,3-bis (isocyanatomethyl) benzene, 1,3-phenylene diisocyanate, 1,4 -Diisocyanatobutane, 1,4-phenylene diisocyanate, 1,6-diisocyanatohexane, 1,8-diisocyanatooctane, 2,4,6-trimethyl-1,3-phenylene diisocyanate, 3,3′-dimethoxy-4,4′-biphenylene diisocyanate, 4-chloro-6-methyl-1,3-phenylene diisocyanate, isophorone diisocyanate, m-xylylene diisocyanate, tolylene diisocyanate (2,4-diisocyanatotolylene, 2,5-diisocyanatotolylene, 2,6-diisocyanatotolylene , Α, 4-diisocyanatotolylene alone or as a mixture), trans-1,4-cyclohexylene diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, 3,3′- Dimethyl-4,4′-biphenylene diisocyanate, 4-bromo-6-methyl-1,3-phenylene diisocyanate, 4,4′-methylene bis (phenyl isocyanate), 4,4′-methylene bis (2- Chlorophenyl isocyanate), 4,4′-methylenebis (2,6-diethylphenyl isocyanate), 4,4′-methylenebis (cyclohexyl isocyanate), 4,4′-oxybis (phenylisocyanate), 1,3- Bis (isocyanatomethyl) cyclohexane, trimethyl-1,6-diisocyanatohexane, etc. Although it is mentioned, it is not limited to these. These compounds can be used alone or in combination of two or more.

  In addition to the (A) polyamideimide represented by the above general formula (I), the polyamideimide having a repeating unit represented by the following general formula (IV) for the purpose of adjusting solubility and various physical properties is also the (A) polyamide of the present invention. It can be used as an imide.

（式中、ｍは１以上の正数であり、ｌ、ｌ’はそれぞれ１〜１００００の正数である。また、式中、Ｕは（２＋ｍ）価の有機基を示し、Ｖは３価の有機基を示し、Ｗは活性水素を有さない２価の有機基を示し、Ｙは２価の有機基を示す。また、Ｒは酸の作用で分解し水素原子に変換し得る、一価のアセタールもしくはケタールを構成する基、アルコキシアルキル基、アルキルシリル基、アルコキシカルボニル基、アルキル基等を示す。）

(In the formula, m is a positive number of 1 or more, l and l ′ are each a positive number of 1 to 10000. In the formula, U represents a (2 + m) -valent organic group, and V is trivalent. W represents a divalent organic group having no active hydrogen, Y represents a divalent organic group, and R can be decomposed and converted to a hydrogen atom by the action of an acid. A group constituting a monovalent acetal or ketal, an alkoxyalkyl group, an alkylsilyl group, an alkoxycarbonyl group, an alkyl group, etc.)

  In the general formula (IV), m, R, U, V, and W are the same as m, R, U, V, and W in the general formula (I), and Y is a diamine having no phenolic hydroxyl group (described later). A residue of a1 ′) can be exemplified. In addition, l and l ′ are each a positive number of 1 to 10,000. In the present invention, when the ratio of l to l ′ (molar fraction) is 1 when the sum of l and l ′ is 1, l ′ is It is preferable that it is 0.4-0, and it is more preferable that it is 0.2-0.

  Examples of the diamine (a1 ′) having no phenolic hydroxyl group 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) ) Aromatic diamine compounds such as biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenoxy) benzene, and other diamines containing a siloxane skeleton, LP- 7100, X-22-161AS, -22-161A, X-22-161B, X-22-161C, and X-22-161E (both Shin-Etsu Chemical Co., Ltd., trade name) does not but like limited thereto. These compounds can be used alone or in combination of two or more.

  There is no restriction | limiting in particular about the synthesis | combining method of (A) polyamideimide shown by the said general formula (I) or (IV), A known method can be used. Specifically, for example, diimide dicarboxylic acid obtained by reacting a diamine having a phenolic hydroxyl group and tricarboxylic acid monoanhydride with a diisocyanate to obtain a phenolic hydroxyl group of a polyamideimide soluble in an alkali aqueous solution. Can be obtained by introducing a protecting group. Alternatively, it may be prepared by other synthesis methods. Of course, diisocyanate (diisocyanate (a1) and triimide monoanhydride (a2) obtained by reacting the above-described phenolic hydroxyl group-containing diamine (a2) with diisocyanate ( It may be synthesized by reacting a3) and further protecting the phenolic hydroxyl group.

  The diimidecarboxylic acid is prepared by using the diamine (a1) having a phenolic hydroxyl group and the tricarboxylic acid monoanhydride (a2) in an organic solvent as necessary (for example, N-methyl-2-pyrrolidone, N-methyl- 2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide, γ-butyrolactone, toluene, benzene and the like). As the diamine (a1) having a phenolic hydroxyl group used in this synthesis, the above-mentioned condensate of a diamine having a phenolic hydroxyl group and a tetracarboxylic dianhydride, or a diamine (a1) having a phenolic hydroxyl group is phenol. In addition, a diamine (a1 ′) having no functional hydroxyl group is further added.

  The imidization is performed by, for example, a method of heating and refluxing using toluene or xylene, and the reaction temperature is preferably 30 to 300 ° C, more preferably 50 to 250 ° C. Moreover, the method of heating in the presence of a base catalyst such as pyridine is also used, and the reaction temperature when using a catalyst is preferably -20 to 200 ° C, more preferably 0 to 150 ° C. The reaction time for imidization is approximately 10 minutes to 10 hours, and the atmosphere may be either air or an inert gas atmosphere, and can be performed in a pressurized or reduced pressure atmosphere in addition to atmospheric pressure. Here, when imidation is performed using toluene or xylene under heating and reflux, the diisocyanate (a3) can be reacted without purifying the diimidecarboxylic acid having a phenolic hydroxyl group.

  When synthesizing the diimidecarboxylic acid, the mixing ratio of the diamine having a phenolic hydroxyl group and the tricarboxylic acid monoanhydride is from 1.6 mol to 2 mol of tricarboxylic acid monoanhydride with respect to 1 mol of the diamine having a phenolic hydroxyl group. .4 moles are preferred, 1.8 moles to 2.2 moles are more preferred, and 1.9 moles to 2.2 moles are even more preferred.

  In the present invention, the diimide carboxylic acid and the diisocyanate (a3) are used in an organic solvent used as necessary (for example, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethyl). Acetamide, N, N-dimethylformamide, γ-butyrolactone, toluene, benzene, etc.) can be polymerized according to a conventional method. In the polymerization reaction, the carboxyl group of diimidecarboxylic acid is added to the isocyanate group of diisocyanate (a3), and then proceeds by thermal decomposition with decarboxylation of the carboxycarbonylamino group to form an amide group. Is. The reaction temperature is preferably 30 to 300 ° C, more preferably 50 to 250 ° C. The reaction time is approximately 10 minutes to 10 hours, and the atmosphere may be either air or an inert gas atmosphere, and can be performed in a pressurized or reduced pressure atmosphere in addition to atmospheric pressure.

  In the polymerization reaction, the mixing ratio of the diimide carboxylic acid and the diisocyanate (a3) is preferably 0.5 to 2.0 mol of diisocyanate with respect to 1 mol of diimide carboxylic acid, and 0.6 mol. To 1.8 mol is more preferable, and 0.7 mol to 1.6 mol is more preferable.

  After the polymerization reaction, the product may be used as it is for the next protection reaction, or may be used for the next protection reaction after reprecipitation in a poor solvent for the polymer (aqueous alkali soluble polyamideimide). it can. Here, the synthesis method (polymerization reaction) is characterized in that only carbon dioxide is produced as a by-product and purification work is not necessarily required. Therefore, the man-hour for preparing the positive photosensitive polyamideimide resin composition can be reduced, and the manufacturing cost can be reduced.

  In order to introduce a protecting group into the polymer (alkaline aqueous solution-soluble polyamideimide) obtained by the above method, this polymer was converted to tetrahydrofuran, N-methylpyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, etc. In the aprotic organic solvent, a structural unit represented by the above general formula (I) or (IV) is obtained by adding a protective agent for a hydroxyl group having R and a reaction catalyst as necessary to carry out a protection reaction. (A) Polyamideimide having

  In the present invention, the protective agent is not particularly limited as long as it is a reactive agent capable of introducing a protective group into the hydroxyl group of the polyamideimide having a phenolic hydroxyl group (alkali aqueous solution-soluble polyamideimide) used in the present invention. Examples thereof include dihydropyran, dihydrofuran, vinyl ethers, alkoxyalkyl halides, silyl halides, carbonates, and chloroformates.

  In the present invention, the reaction temperature for protection is preferably -100 to 300 ° C, more preferably -80 to 250 ° C. The reaction time is approximately 10 minutes to 10 hours, and the atmosphere may be either air or an inert gas atmosphere, and can be performed in a pressurized or reduced pressure atmosphere in addition to atmospheric pressure. The product is re-precipitated in a poor solvent, if necessary, and then isolated and purified through filtration and drying.

  The molecular weight of the polyamideimide (A) represented by the above general formula (I) or (IV) thus obtained is determined by the solubility, photosensitivity of the deprotected body (that is, the aqueous alkaline solution soluble polyamideimide) in the alkaline aqueous solution. Considering the balance between properties and cured film properties, the weight average molecular weight is preferably 3,000 to 200,000, more preferably 5,000 to 100,000. Here, the molecular weight is a value obtained by measuring by a gel permeation chromatography method and converting from a standard polystyrene calibration curve.

In addition, the introduction ratio of the protecting group represented by R in the (A) polyamideimide represented by the general formula (I) or (IV) is preferably 5 to 95%, more preferably 10 to 90%. More preferred. If the replacement rate is higher than this, the adhesion to the substrate will be reduced, and if the replacement rate is lower than this, there will be adverse effects such as increased film loss in unexposed areas There is.
Here, the “introduction rate of the protecting group” in the present invention refers to the number of functional groups (OR groups) into which the protecting group has been introduced and the functional group in which the protecting group has not been introduced (OH) in the (A) polyamideimide of the present invention. The ratio of the number of functional groups (OR groups) introduced with protecting groups to the total number of groups) is expressed as a percentage. That is, the protective group introduction rate [%] = [OR group mole number / (OR group mole number + OH group mole number) × 100]. Specifically, the introduction rate of the protecting group can be calculated using a known analysis method such as an NMR spectrum or an IR spectrum.

[(B) Compound that generates acid upon irradiation]
The compound (acid generator) that generates an acid upon irradiation with radiation (B) used in the present invention exhibits acidity upon irradiation with an actinic ray such as ultraviolet rays, and also has a phenolic hydroxyl group of the polyamideimide as the component (A). It has the effect of removing the protecting group R. Further, in the present invention, (B) the acid generator is added as necessary (D) conversion action of a compound having an organic group that can be converted to carboxylic acid by acid catalysis (specifically, a soluble conversion agent). Also have.

  Examples of such a component (B) compound include onium salts such as diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic N-oxyimide sulfonates, or Oxime esters such as oxime sulfonic acid esters and oxime carboxylic acid esters (O-acyl oximes) are used. Furthermore, use of aromatic tetracarboxylic acid ester, aromatic sulfonic acid ester, nitrobenzyl ester, aromatic sulfamide, haloalkyl group-containing hydrocarbon compound, haloalkyl group-containing heterocyclic compound, naphthoquinonediazide-4-sulfonic acid ester, etc. You can also. Two or more kinds of such compounds can be used in combination as needed, or can be used in combination with other sensitizers.

Among them, aromatic N-oxyimide sulfonate or oxime ester is preferable because diaryliodonium salt can be expected to have an appropriate dissolution inhibitory effect in the unexposed area.
Here, in addition to the above-described ultraviolet rays, for example, X-rays, electron beams, visible rays and the like can be used as the actinic rays. In particular, a wavelength of 200 nm to 500 nm is preferable. Also, monochromatic light such as g-line or i-line can be used.

  In the positive photosensitive polyamideimide resin composition of the present invention, the blending amount of the component (B) is 0.01% with respect to 100 parts by weight of the component (A) in order to improve the sensitivity and resolution during exposure. -50 parts by weight, preferably 0.01-20 parts by weight, and more preferably 0.5-15 parts by weight.

[(C) Solvent]
Examples of the solvent (C) used in the present invention include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, and 3-methylmethoxypropionate. N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, propylene glycol monomethyl Examples include ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and the like.
These solvents can be used alone or in combination of two or more. Moreover, the compounding amount of the component (C) is not particularly limited, but generally it is preferably adjusted so that the proportion of the solvent in the positive photosensitive polyamideimide resin composition is 20 to 90% by weight.

[(D) Compound having an organic group that can be converted to carboxylic acid or phenolic hydroxyl group by acid catalysis]
In the present invention, in addition to the components (A) to (C), for the purpose of improving the contrast by the dissolution inhibiting effect in the unexposed area and the dissolution promoting effect in the exposed area, (D) a carboxylic acid by acid catalysis Alternatively, a compound having an organic group that can be converted into a phenolic hydroxyl group (hereinafter simply referred to as the component (D) can be added as necessary).

The component (D) used in the present invention is not particularly limited as long as it has an organic group that can be converted into a carboxylic acid or a phenolic hydroxyl group by acid catalysis.
First, among the component (D) used in the present invention, a compound having an organic group that can be converted into a carboxylic acid by acid catalysis is a group represented by —COOQ in the molecule (provided that Q is decomposed by the action of an acid). And a compound having a monovalent organic group that can be converted into a hydrogen atom) is preferable in terms of conversion efficiency.
A preferable compound having an organic group that can be converted into a carboxylic acid by acid catalysis is represented by the following general formula (V), but is not limited to the following.

  Here, Y in the general formula (V) is specifically diphenyl, diphenyl ether, diphenylthioether, benzophenone, diphenylmethane, diphenylpropane, diphenylhexafluoropropane, diphenylsulfoxide, diphenylsulfone, benzene, naphthalene, perylene, etc. Examples thereof include aromatic hydrocarbon residues having a skeleton, aliphatic hydrocarbon residues having a skeleton such as butane, cyclobutane, cyclohexane and adamantane, or those having a structure represented by the following general formula (VI). In addition, pp shows a polymer.

（式中、Ｚ、Ｚ’はアルキル基あるいはアルキル置換又は無置換のヘテロ原子を示す。）

(In the formula, Z and Z ′ represent an alkyl group or an alkyl-substituted or unsubstituted heteroatom.)

Q in the general formula (V) represents a monovalent organic group that can be decomposed and converted into a hydrogen atom by the action of an acid.
As the monovalent group Q that can be decomposed by this acid catalysis and converted into a hydrogen atom, the group constituting the monovalent acetal or ketal exemplified in the above-mentioned group R, an alkoxyalkyl group, and an alkylsilyl group are preferable. Can be mentioned.

  Next, among the component (D) used in the present invention, a compound having an organic group that can be converted into a phenolic hydroxyl group by acid catalysis is a group represented by -OQ 'in the molecule (provided that -OQ' is A compound having a monovalent organic group which is bonded to an aromatic ring and can be decomposed by the action of an acid and converted into a hydrogen atom is preferable from the viewpoint of conversion efficiency. A compound having an organic group that can be converted to a phenolic hydroxyl group by such an acid catalyst action is a compound having a phenolic hydroxyl group (bonded to an aromatic ring and represented by —OH) with Q ′. Protected.

  Examples of the monovalent organic group Q ′ that can be decomposed by the action of an acid and converted into a hydrogen atom include a group constituting a monovalent acetal or ketal exemplified in the above-mentioned group R, an alkoxyalkyl group, an alkylsilyl group, an alkoxycarbonyl Groups and alkyl groups can be mentioned as preferred.

Examples of the compound having a phenolic hydroxyl group include alkali-soluble resins such as polyvinylphenol, phenols, bisphenols, trisphenols, trisphenol alkanes, trinuclear phenol resins, and tetrakisphenols. .
Examples of the compound having an organic group that can be converted to a phenolic hydroxyl group by such an acid catalyst action include compounds having an acid-decomposable group that increases solubility in an alkaline aqueous solution by an acid-catalyzed reaction described in Japanese Patent No. 3755382. can do.

  The blending amount of the component (C) is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the component (A) when the component (C) is an oligomer or polymer from the viewpoint of sensitivity and film quality after curing. It is more preferable to set it as 5-100 weight part. In other cases, the amount is preferably 1 to 50 parts by weight, more preferably 1 to 25 parts by weight with respect to 100 parts by weight of component (A).

  In the positive photosensitive polyamideimide resin composition of the present invention, in addition to the components (A) to (C) and (D), (1) a crosslinking agent, (2) a dissolution accelerator, and (3) a dissolution inhibitor. Components such as (4) coupling agent and (5) surfactant may be blended.

[Other components: (1) Crosslinking agent]
In the present invention, as (1) the crosslinking agent, a compound having an epoxy group or a compound having a phenolic hydroxyl group can be used as a particularly preferable one. Among these, the compound having a phenolic hydroxyl group increases the dissolution rate of the exposed area when developing with an alkaline aqueous solution by mixing, and the sensitivity increases, and also reacts with polyamideimide when the film after pattern formation is cured, That is, it is bridged. This is preferable because brittleness of the film and melting of the film can be prevented.

  The compound having a phenolic hydroxyl group that can be used in the present invention is not particularly limited, but a compound having a molecular weight of 1,500 or less is generally preferred because the effect of promoting dissolution of an exposed area is reduced when the molecular weight is increased. Among them, those represented by the following general formula (VII) are particularly preferred because they are excellent in the balance between the effect of promoting dissolution of the exposed area and the effect of preventing melting during curing of the film.

（式中、Ｘはその両側の２つのベンゼン環を繋ぐ単なる結合（即ちＸとしては何もなし）又は２価の有機基を示し、Ｒ¹〜Ｒ⁴は各々独立に水素原子又は一価の有機基を示し、α及びβは各々独立に１〜３の整数であり、γ及びδは各々独立に０〜４の整数である。）

(In the formula, X represents a simple bond connecting two benzene rings on both sides thereof (that is, nothing as X) or a divalent organic group, and R ^{1 to} R ⁴ each independently represents a hydrogen atom or a monovalent group) Represents an organic group, α and β are each independently an integer of 1 to 3, and γ and δ are each independently an integer of 0 to 4).

  In the general formula (VII), the compound in which X is a mere bond connecting two benzene rings on both sides thereof (that is, nothing as X) is specifically a biphenol (dihydroxybiphenyl) derivative. Examples of the divalent organic group represented by X include alkylene groups having 1 to 10 carbon atoms such as methylene group, ethylene group and propylene group, alkylidene groups having 2 to 10 carbon atoms such as ethylidene group, and phenylene groups. Arylene groups having 6 to 30 carbon atoms, such as 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 bonds Etc.

  As (1) a crosslinking agent used in the present invention, a compound similar to a compound having a phenolic hydroxyl group can be added. Compounds similar to the compound having a phenolic hydroxyl group increase the sensitivity by increasing the dissolution rate of the exposed area when developing with an alkaline aqueous solution, and the film melts when the film is cured after pattern formation. Can be prevented. Furthermore, when a compound similar to a compound having a phenolic hydroxyl group is used as (1) a crosslinking agent, a pattern excellent in sensitivity, resolution and adhesiveness and excellent in physical properties such as heat resistance can be obtained. As such a compound, a compound represented by the following chemical formula (VIII) can be exemplified.

  In the positive photosensitive polyamideimide resin composition of the present invention, (1) the compounding amount of the crosslinking agent is based on 100 parts by weight of component (A) from the viewpoint of the development time and the allowable width of the unexposed part residual film ratio. 1 to 30 parts by weight is preferable, and 2 to 25 parts by weight is more preferable.

[Other components: (2) Dissolution promoter]
In the present invention, the dissolution accelerator (2) is a compound that improves the solubility of the component (A) in an alkaline aqueous solution. Although there is no restriction | limiting in particular as such a compound, Specifically, it is a compound which has a carboxyl group, a sulfonic acid, a sulfonamide group, and a phenolic hydroxyl group. Among these, the compound having a phenolic hydroxyl group represented by the general formula (VII) is preferable in that it has both (1) an effect as a crosslinking agent and (2) an effect as a dissolution accelerator during curing.

In the positive photosensitive polyamideimide resin composition of the present invention, the blending amount of the dissolution accelerator (2) component is determined by the dissolution rate in the alkaline aqueous solution, but is generally 0 with respect to 100 parts by weight of the component (A). 0.01 to 30 parts by weight.
As described above, for example, some compounds having a phenolic hydroxyl group have both a function as a crosslinking agent (1) and a function as a dissolution accelerator (2). If such a compound having the functions of component (1) and component (2) is used, it is not necessary to separately use component (1) and component (2). In this case, the compounding amount of the compound having both functions of the component (1) and the component (2) is (A) component 100 from the viewpoint of the development time, the allowable range of the unexposed portion remaining film ratio, and the dissolution promoting effect at the time of development. 1 to 30 parts by weight is preferable with respect to parts by weight, and 2 to 25 parts by weight is more preferable.

[Other components: (3) Dissolution inhibitor]
In the present invention, the (3) dissolution inhibitor is a compound that inhibits the solubility of the component (A) in the alkaline aqueous solution, and can be contained in the positive photosensitive polyamideimide resin composition. Specific examples include diphenyliodonium nitrate, bis (pt-butylphenyl) iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, and diphenyliodonium iodide. These are useful for controlling the remaining film thickness and development time. The blending amount of the above components is preferably 0.01 to 20 parts by weight, more preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of component (A), from the viewpoint of sensitivity and an allowable range of development time. 0.05 to 10 parts by weight is more preferable.

[Other components: (4) Coupling agent]
The positive photosensitive polyamide-imide resin composition of the present invention can contain a coupling 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, urea propyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, n- Propylphenylsilanediol, isopropylphenylsilanediol, n-butylsiphenylsilanediol, isobutylphenylsilanediol, t-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol , N-butylmethylphenylsilanol, isobutylmethylphenylsilanol, t-butylmethylphenylsilanol, ethyl n -Propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, t-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyl Diphenylsilanol, 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 (butyldihydroxysilyl) , 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropyldroxysilyl) benzene, 1,4-bis (dibutylhydroxysilyl) Examples include benzene. When using these coupling 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.

[Other components: (5) Surfactant]
In addition, the positive photosensitive polyamideimide resin composition of the present invention is added with an appropriate surfactant or leveling agent in order to prevent coatability, for example, 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 (Dainippon Ink Chemical Co., Ltd. product name), Florard FC430, FC431 (Sumitomo 3M Co., Ltd. product name), Organosiloxane polymer KP341, KBM303, KBM403, KBM803 (Product made by Shin-Etsu Chemical Co., Ltd.) Name).

[Pattern manufacturing method]
Next, a pattern manufacturing method according to the present invention will be described. The method for producing a pattern of the present invention includes a step of applying the positive photosensitive polyamideimide resin composition described above on a support substrate and drying, a step of exposing the photosensitive resin film obtained by the drying step, Preferably, the step of heating the photosensitive resin film after exposure, the step of developing the photosensitive resin film after exposure using an alkaline aqueous solution, and the step of heat-treating the photosensitive resin film after development including. Hereinafter, each step will be described.

(Coating / drying (film formation) process)
First, in the step of applying and drying a positive photosensitive polyamideimide resin composition on a support substrate, on a support substrate such as a glass substrate, a semiconductor, a metal oxide insulator (eg, TiO ₂ , SiO _2, etc.) or silicon nitride. In addition, the above-described positive photosensitive polyamideimide resin composition is spin-coated using a spinner or the like, and then the support substrate is dried using a hot plate, an oven, or the like. Thereby, a film of the positive photosensitive polyamideimide resin composition, that is, a photosensitive resin film is formed on the support substrate.

(Exposure process)
Next, in the exposure step, the 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, about the photosensitive polyamide imide resin composition using the polyamide imide with high transparency with respect to i line | wire among the polyamide imides used for this invention, irradiation of i line | wire can be used suitably.

(Post-exposure heating process)
For the purpose of diffusing the acid generated in the surface portion of the irradiated portion to the bottom, it is preferable to perform post-exposure heating (PEB) and then proceed to the development step. The post-exposure heating temperature is preferably 50 ° C. to 150 ° C., and the post-exposure heating time is preferably 1 minute to 10 minutes.

(Development process)
In the development step, a pattern is obtained by removing the exposed portion of the photosensitive polyamideimide resin composition exposed to actinic rays with a developer. As the developer, for example, alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide and the like are preferable. 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, a pattern of polyamideimide can be formed by heat-treating the pattern obtained after development. The heating temperature in the heat treatment step is 250 ° C. or less, desirably 200 ° C. or less, and more desirably 140 to 200 ° C.

  The heat treatment is performed using a quartz tube furnace, hot plate, rapid thermal annealing, vertical diffusion furnace, infrared curing furnace, electron beam curing furnace, 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 process under nitrogen because the oxidation of the photosensitive polyamideimide 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. Furthermore, since the positive photosensitive polyamide-imide resin of the present invention has a small volume shrinkage (curing shrinkage) in the heat treatment step found in conventional photosensitive polyimide and the like, it is possible to prevent a reduction in dimensional accuracy. Therefore, a pattern having excellent dimensional stability can be obtained.

  The heat treatment time in the heat treatment step of the present invention is a time until the positive photosensitive polyamide-imide resin composition is cured, for example, a time until the crosslinking reaction sufficiently proceeds. Approximately 5 hours or less is preferable.

(Microwave curing)
As the heat treatment in the heat treatment step of the pattern manufacturing method, a microwave curing device or a variable frequency microwave curing device can be used in addition to using an ordinary nitrogen-substituted oven. By using these, it is possible to effectively heat only the photosensitive polyamide-imide resin composition film while keeping the temperature of the substrate or device at, for example, 200 ° C. or lower.

  In the variable frequency microwave curing apparatus, the microwave is irradiated in pulses while changing its frequency, so that standing waves can be prevented and the substrate surface can be heated uniformly. In addition, when a metal wiring is included as an electronic component to be described later as a substrate, the occurrence of discharge from the metal can be prevented by irradiating microwaves in a pulsed manner while changing the frequency, and the electronic component is protected from destruction. It is preferable in that it can be performed. Furthermore, heating using a frequency-variable microwave is preferable because the cured film properties do not deteriorate even when the curing temperature is lowered as compared to an oven (see J. Photopolym. Sci. Technol., 18, 327-332 (2005)). .

  The frequency of the frequency variable microwave 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. In addition, it is desirable to continuously change the frequency of the microwave to be irradiated, but actually the irradiation is 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.

  Moreover, it is preferable to irradiate the microwave by turning it on / off in a pulsed manner. By irradiating the microwaves in a pulsed manner, it is preferable in that the set heating temperature can be maintained and damage to the cured 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 preferably about 10 seconds or less.

[Semiconductor device manufacturing process]
Next, as an example of a pattern manufacturing method according to the present invention, a semiconductor device manufacturing process will be described with reference to the drawings. 1A to 1E are schematic cross-sectional views for explaining a manufacturing process of a semiconductor device having a multilayer wiring structure. 1-1 to 1-5, 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. A first conductor layer 3 is formed on the exposed circuit element. An interlayer insulating film 4 such as a polyimide resin is formed on the semiconductor substrate 1 by a spin coat method or the like (FIG. 1-1).

  Next, a photosensitive resin layer 5 such as chlorinated rubber or phenol novolac is formed on the interlayer insulating film 4 as a mask by a spin coating method, and a predetermined portion of the interlayer insulating film 4 is formed by a known photolithography technique. A window 6A is provided so as to be exposed (FIG. 1-2). The interlayer insulating film 4 in the window 6A is selectively etched by 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 (FIGS. 1-3). 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 (FIGS. 1-4).

  Next, the surface protective film 8 is formed. In the example of FIGS. 1-1 to 1-5, the positive photosensitive polyamideimide resin composition according to the present invention is applied onto the interlayer insulating film 4 and the second conductor layer 7 by a spin coat method and dried. Next, after irradiating light from a mask on which a pattern for forming a window 6C is formed in a predetermined portion, the exposed photosensitive resin film is preferably heated, and further developed with an alkaline aqueous solution to form a pattern. . Then, it heats (hardens) and forms the polyamideimide film as the surface protective film 8 (FIGS. 1-5). This polyamideimide film protects the conductor layer from external stress, α-rays, etc., and the obtained semiconductor device is excellent in reliability.

  When a multilayer wiring structure having three or more layers is formed, each layer can be formed by repeating the above steps. That is, it is possible to form a multilayer pattern by repeating each step of forming the interlayer insulating film 4 and each step of forming the surface protective film 8. In the above example, not only the surface protective film 8 but also the interlayer insulating film 4 can be formed using the positive photosensitive polyamideimide resin composition of the present invention.

[Electronic parts]
Next, the electronic component according to the present invention will be described. The electronic component according to the present invention has a pattern formed by the above-described pattern manufacturing method using a positive photosensitive polyamideimide resin composition. Here, the electronic component includes a semiconductor device, a multilayer wiring board, various electronic devices, and the like. Further, the pattern can be used specifically for forming a surface protective film, an interlayer insulating film of a semiconductor device, an interlayer insulating film of a multilayer wiring board, and the like. 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 composition, and can have various structures.

[Other structures]
Further, since the positive photosensitive polyamideimide resin composition of the present invention is excellent in stress relaxation, adhesion, chemical resistance, etc., it can also be used as various structural materials in variously developed packages having recently been developed. Can do. 2 and 3 show a cross-sectional structure of an example of such a semiconductor device.

  FIG. 2 is a schematic cross-sectional view showing the multilayer wiring structure of the semiconductor device. In FIG. 2, an Al wiring layer 12 is formed on the interlayer insulating layer 11, and an insulating layer 13 (for example, P- SiN layer) is formed, and a surface protective film layer 14 of the element is further formed. A rewiring layer 16 is formed from the pad portion 15 of the Al wiring layer 12, and the rewiring layer 16 is a core 18 which is a connection portion with a conductive ball 17 formed of solder, gold or the like as an external connection terminal. It extends to the top of the. Further, a cover coat layer 19 is formed on the surface protective film layer 14. The rewiring layer 16 is connected to the conductive ball 17 through the barrier metal 20, and a collar 21 is provided to hold the conductive ball 17. When a package having such a structure is mounted, an underfill 22 may be formed around the conductive ball 17 in order to further relieve stress.

  FIG. 3 is a schematic cross-sectional view showing the wiring structure of the semiconductor device. In FIG. 3, an Al wiring layer (not shown) and a pad portion 15 of the Al wiring layer are formed on the silicon chip 23, and an upper portion thereof. An insulating layer 13 is formed, and a surface protective film layer 14 of the element is further formed. Similar to FIG. 2, a rewiring layer 16 is formed from the pad portion 15, and this rewiring layer 16 extends to an upper portion of the connection portion 24 with the conductive ball 17. Further, a cover coat layer 19 is formed on the surface protective film layer 14. The rewiring layer 16 is connected to the conductive ball 17 through the barrier metal 20.

  2 and 3, the positive photosensitive polyamideimide resin composition of the present invention includes not only the interlayer insulating layer 11 and the surface protective film layer 14 but also the cover coat layer 19, the core 18, the collar 21, the underfill. It can be used as a material such as 22. The cured resin using the positive-type photosensitive polyamideimide resin composition of the present invention is excellent in adhesion to metal layers such as the Al wiring layer 12 and the rewiring layer 16, sealants, etc., and has a high stress relaxation effect. Therefore, a semiconductor device using this cured body for the cover coat layer 19, the rewiring core 18, the ball collar 21 such as solder, the underfill 12 used in a flip chip, etc. has extremely high reliability. .

  As described above, by using the positive photosensitive polyamide-imide resin composition according to the present invention, in the above heat treatment process that conventionally required 300 ° C. or higher, curing using low-temperature heating of 200 ° C. or lower is possible. Is possible. Moreover, since the photosensitive polyamideimide resin of the present invention has a small volume shrinkage (curing shrinkage) in the heat treatment step found in conventional photosensitive polyimide and the like, it is possible to prevent a reduction in dimensional accuracy. The cured film of the positive photosensitive polyamideimide resin composition has a high glass transition temperature. Therefore, the surface protective film is excellent in heat resistance. As a result, an electronic component such as a semiconductor device having excellent reliability can be obtained with high yield and high yield.

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

Synthesis Example 1 Synthesis of Polyamideimide In a 0.5 liter flask equipped with a stirrer, a thermometer, a reflux tube, and a Dean-Stark type moisture receiver, 2,2-bis (3-amino-4-hydroxy Phenyl) -1,1,1,3,3,3-hexafluoropropane (5.49 g) and trimellitic anhydride (6.05 g) were dissolved in N-methylpyrrolidone (50 g). This solution was heated to 80 ° C. and reacted for 30 minutes. Next, 30 ml of toluene was added, and after heating at 160 ° C. for 2 hours, the temperature was further raised to 180 ° C. to distill off the toluene. The reaction solution was cooled, and 3.00 g of 4,4′-methylenebis (phenyl isocyanate) was further added, followed by reaction at 150 ° C. for 2 hours. The reaction solution was cooled, and 2.52 g of 2,3-dihydro-2H-pyran and a catalytic amount of p-toluenesulfonic acid were added and reacted at room temperature for 1 hour. The reaction product was poured into 1 liter of water, and the precipitate was collected, washed with pure water, and then dried under reduced pressure to obtain polyamideimide (hereinafter referred to as polymer A1). The polymer A1 had a weight average molecular weight of 33,000 and a dispersity of 1.7 determined by GPC standard polystyrene conversion. Further, the introduction rate of the protecting group was 87%.

Synthesis Example 2 Synthesis of Polyamideimide In a 0.5 liter flask equipped with a stirrer, a thermometer, a reflux tube, and a Dean-Stark type moisture receiver, 2,2-bis (3-amino-4-hydroxy Phenyl) -1,1,1,3,3,3-hexafluoropropane (5.49 g) and 1,2,4-tricarboxycyclohexane-1,2-anhydride (6.24 g) to N-methylpyrrolidone (50 g) Dissolved. This solution was heated to 80 ° C. and reacted for 30 minutes. Next, 30 ml of toluene was added, and after heating at 160 ° C. for 4 hours, the temperature was further raised to 180 ° C. to distill off the toluene. The reaction solution was cooled, and 2.87 g of tolylene diisocyanate (a mixture of 2,4-diisocyanatotolylene and 2,6-diisocyanatotolylene) was added and reacted at 150 ° C. for 2 hours. The reaction solution was cooled, and 2.52 g of 2,3-dihydro-2H-pyran and a catalytic amount of p-toluenesulfonic acid were added and reacted at room temperature for 1 hour. The reaction product was poured into 1 liter of water, and the precipitate was collected, washed with pure water, and then dried under reduced pressure to obtain polyamideimide (hereinafter referred to as polymer A2). The polymer A2 had a weight average molecular weight of 38,000 and a dispersity of 2.2 determined by GPC standard polystyrene conversion. Further, the introduction rate of the protecting group was 85%.

(Synthesis example 3) The synthesis | combination of a polyamidoimide Like Example 2, 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane 5.49g 1,2,4-tricarboxycyclohexane-1,2-anhydride 6.24 g and tolylene diisocyanate 2.87 g were added, and then chloromethyl methyl ether 2.17 g and potassium carbonate were added. For 2 hours. The reaction product was poured into 1 liter of water, and the precipitate was collected, washed with pure water, and then dried under reduced pressure to obtain polyamideimide (hereinafter referred to as polymer A3). The polymer A3 had a weight average molecular weight of 37,000 and a dispersity of 2.5 determined by GPC standard polystyrene conversion. Further, the introduction rate of the protecting group was 80%.

(Synthesis Example 4) Synthesis of Polyamideimide In the same manner as in Example 2, 2,49-gram of 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane , 1,2,4-tricarboxycyclohexane-1,2-anhydride 6.24 g and tolylene diisocyanate 2.87 g were reacted, 4.07 g of tert-butyldimethylsilyl chloride and imidazole were added, The reaction was allowed to proceed for 3 hours at room temperature. The reaction product was poured into 1 liter of water, and the precipitate was collected, washed with pure water, and then dried under reduced pressure to obtain polyamideimide (hereinafter referred to as polymer A4). The polymer A4 had a weight average molecular weight of 35,000 and a dispersity of 2.1 determined by GPC standard polystyrene conversion. Further, the introduction rate of protective groups was 82%.

(Synthesis Example 5) Synthesis of Polyamideimide In the same manner as in Example 2, 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane 5.49 g , 1,2,4-tricarboxycyclohexane-1,2-anhydride 6.24 g and tolylene diisocyanate 2.87 g, 6.54 g of di-tert-butyl dicarbonate and a catalytic amount 4- (dimethylamino) pyridine was added and reacted at room temperature for 3 hours. The reaction product was poured into 1 liter of water, and the precipitate was collected, washed with pure water, and then dried under reduced pressure to obtain polyamideimide (hereinafter referred to as polymer A5). The polymer A5 had a weight average molecular weight of 35,000 and a dispersity of 2.5 determined by GPC standard polystyrene conversion. Further, the introduction rate of the protecting group was 90%.

Synthesis Example 6 Synthesis of Polyamideimide In a 0.5 liter flask equipped with a stirrer, a thermometer, a reflux tube, and a Dean-Stark type water receiver, 2,2-bis (3-amino-4-hydroxy (Phenyl) -1,1,1,3,3,3-hexafluoropropane (10.98 g) and oxydiphthalic dianhydride (4.65 g) were dissolved in N-methylpyrrolidone (50 g). This solution was heated to 80 ° C. and reacted for 30 minutes. Next, 30 ml of toluene was added, and after heating at 160 ° C. for 3 hours, the temperature was further raised to 180 ° C. to distill off the toluene. The reaction solution was cooled, 6.24 g of 1,2,4-tricarboxycyclohexane-1,2-anhydride was added, and the solution was heated to 80 ° C. and reacted for 30 minutes. Next, 30 ml of toluene was added, and after heating at 160 ° C. for 4 hours, the temperature was further raised to 180 ° C. to distill off the toluene. The reaction liquid was cooled, and 3.13 g of tolylene diisocyanate (a mixture of 2,4-diisocyanatotolylene and 2,6-diisocyanatotolylene) was added, followed by reaction at 150 ° C. for 2 hours. The reaction solution was cooled, and 5.04 g of 2,3-dihydro-2H-pyran and a catalytic amount of p-toluenesulfonic acid were added and reacted at room temperature for 1 hour. The reaction product was poured into 1 liter of water, and the precipitate was collected, washed with pure water, and then dried under reduced pressure to obtain polyamideimide (hereinafter referred to as polymer A6). The polymer A6 had a weight average molecular weight of 40,000 and a dispersity of 2.1 determined by GPC standard polystyrene conversion. Further, the introduction rate of the protecting group was 88%.

(Synthesis Example 7) Synthesis of Polyamideimide In the same manner as in Example 2, 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane 10.98 g Oxydiphthalic dianhydride 4.65 g, 1,2,4-tricarboxycyclohexane-1,2-anhydride 6.24 g, tolylene diisocyanate 3.13 g, 13.08 g of natto and a catalytic amount of 4- (dimethylamino) pyridine were added and reacted at room temperature for 3 hours. The reaction product was put into 1 liter of water, and the precipitate was collected, washed with pure water, and then dried under reduced pressure to obtain polyamideimide (hereinafter referred to as polymer A7). The polymer A7 had a weight average molecular weight of 41,000 and a dispersity of 2.5 determined by GPC standard polystyrene conversion. Further, the introduction rate of the protecting group was 85%.

(Examples 1 to 9) Preparation and characterization of positive photosensitive polyamideimide resin composition
In 100 parts by weight of the polyamide aqueous solution [(A) component] soluble in alkaline aqueous solution in blending synthesis examples 1 to 7, the acid generator (B) and the solvent (C) are blended in the predetermined amounts shown in Table 1. Further, 5 parts by weight of a 50% methanol solution of urea propyltriethoxysilane was added as an adhesion assistant. Moreover, the compound (D) which has an organic group which can be converted into carboxylic acid by an acid catalyst action, and the crosslinking agent were mix | blended as needed. This solution was subjected to pressure filtration using a 3 μm pore Teflon (registered trademark) filter to obtain a positive photosensitive polyamideimide resin composition solution (M1 to M9).

  About Examples 1-9, the said (A)-(C) component and the crosslinking agent were mix | blended as shown in Table 1. That is, the component (A) uses the polymers A1 to A7 synthesized in Synthesis Examples 1 to 7, and the component (B) is 9,10-dimethoxy-2-anthracenesulfonic acid diphenyliodonium salt (DIAS) as B1. 1,2-Naphthalimidyl triflate is used as B2, and 2- (4-methoxyphenyl) -2-p-toluenesulfonyloxyiminoacetonitrile (Midori Chemical Co., Ltd., trade name PAI-101) is used as B3 ) Were used. As component (C), γ-butyrolactone / propylene glycol monomethyl ether acetate = 90/10 (weight ratio) was used as C1. As component (D), tris (trimethyl) trimethyl (ethoxymethyl) was used as D1. As the cross-linking agent, trade name TML-BPAF [(1) -1] manufactured by Honshu Chemical Industry Co., Ltd. was used. The composition of Comparative Example 1 will be described later.

Photosensitive characteristics A solution (M1 to M9) of the positive photosensitive polyamideimide resin composition was spin-coated on a silicon substrate and heated at 120 ° C. for 3 minutes to form a coating film having a thickness of 11 to 13 μm. Thereafter, reduction projection exposure was performed with i-line (365 nm) through a mask using an i-line stepper (FPA-3000iW manufactured by Canon). The coating film of the resin M1 was further subjected to reduced projection exposure with g-line (436 nm) through a mask using a g-line stepper (Canon FPA-1550MARK II). The coated film after exposure is heated at 120 ° C. for 3 minutes, developed with a 2.38% aqueous solution of tetramethylammonium hydroxide, and developed so that the residual film thickness is about 70 to 90% of the initial film thickness. went. Thereafter, the film was rinsed with water, and the minimum exposure and resolution required for pattern formation were determined. The results are shown in Table 2.

Patterning of Sample for Measuring Film Physical Properties Further, the positive photosensitive polyamideimide resin composition solution (M1 to M9) was spin-coated on a silicon substrate, heated at 120 ° C. for 3 minutes, and a coating film having a thickness of about 15 μm. Formed. Then, the coating film of resin M1-M9 was exposed through the mask using the proximity exposure machine (PLA-600FA made from Canon). The coated film after exposure was heated at 120 ° C. for 3 minutes and developed with a 2.38% aqueous solution of tetramethylammonium hydroxide to obtain a 10 mm wide rectangular pattern. Thereafter, the coating film was heat-treated (cured) by the following method.

Curing and curing were performed by the following method to obtain a cured film having a thickness of about 10 μm.
(I) Using a vertical diffusion furnace (μ-TF manufactured by Koyo Thermo Systems Co., Ltd.), the coating film was heat-treated in nitrogen at a temperature of 200 ° C. (temperature increase time: 1.5 hours) for 1 hour. (Ii) Frequency variable type Using a microwave curing furnace (Microcure 2100, manufactured by Lambda Technology Co., Ltd.), microwave treatment was 450 W, microwave frequency was 5.9 to 7.0 GHz, temperature was 175 ° C. (heating time 5 minutes), and heat treatment was performed for 2 hours.
Table 3 shows the shrinkage ratio of the film thickness before and after curing ((1-film thickness after curing / film thickness before curing) × 100 [%]).

Film Properties A cured film having a thickness of about 10 μm cured by the above method was peeled from the silicon substrate, and the glass transition temperature (Tg) of the peeled film was measured with TMA / SS600 manufactured by Seiko Instruments Inc. Note that the width of the sample is 2 mm, the film thickness is 9 to 11 μm, and the distance between chucks is 10 mm. The load is 10 g, and the rate of temperature increase is 5 ° C./min. Further, the average breaking elongation (EL) of the release film was measured by an autograph AGS-H100N manufactured by Shimadzu Corporation. The width of the sample is 10 mm, the film thickness is 9 to 11 μm, and the distance between chucks is 20 mm. The pulling speed is 5 mm / min, and the measurement temperature is about room temperature (20 ° C. to 25 ° C.). Here, let the average of five or more measured values be "average breaking elongation (EL)" about the cured film obtained on the same conditions. Table 3 shows the curing conditions, Tg, and EL.

(Comparative synthesis example) Synthesis of polyamide (protector of polybenzoxazole precursor) In a 0.5 liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4'-diphenyl ether dicarboxylic acid, N-methylpyrrolidone After charging 90 g and cooling the flask to 5 ° C., 12.64 g of thionyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of 4,4′-diphenyl ether tetracarboxylic acid chloride. Next, in a 0.5 liter flask equipped with a stirrer and a thermometer, 87.5 g of N-methylpyrrolidone was charged, and 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1, After adding 3.30 g of 3,3,3-hexafluoropropane and stirring and dissolving, 8.53 g 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 stirring was continued for 30 minutes. 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 polyhydroxyamide (polybenzoxazole precursor).

  Next, 30 g of the obtained polyhydroxyamide was dissolved in tetrahydrofuran (100 ml), 6.50 g of 2,3-dihydro-2H-pyran and a catalytic amount of p-toluenesulfonic acid were added and reacted at room temperature for 1 hour. . The reaction product was poured into 1 liter of water, and the precipitate was collected, washed with pure water, and then dried under reduced pressure to obtain polyamide (hereinafter referred to as polymer α). The polymer α had a weight average molecular weight of 16,000 determined by GPC standard polystyrene conversion, and the dispersity was 1.6. Further, the introduction rate of the protecting group was 80%.

(Comparative Example 1)
9,100-dimethoxy-2-anthracenesulfonic acid diphenyliodonium salt B1 as the acid generator (B) and γ-butyrolactone / propylene as the solvent (C) with respect to 100 parts by weight of the polyamide [component (A)] in the comparative synthesis example Glycol monomethyl ether acetate (C1) was blended as shown in Table 1. Further, 5 parts by weight of a 50% methanol solution of urea propyltriethoxysilane was added as an adhesion aid. This solution was subjected to pressure filtration using a 3 μm pore Teflon (registered trademark) filter to obtain a positive photosensitive resin composition solution (M10). The blending amounts are also shown in Table 1. Subsequently, the photosensitive characteristics were examined in the same manner as in Examples 1 to 9, and the results are also shown in Table 2. Furthermore, the physical properties of the cured films were measured in the same manner as in Examples 1 to 9, and the results are also shown in Table 3.

[Examination of results]
Photosensitivity characteristics are summarized in Table 2. As is clear from this, the positive photosensitive polyamideimide resin compositions M2 to M9 (Examples 2 to 9) of the present invention have sensitivity and i-line exposure (365 nm). The resolution was high. On the other hand, the positive photosensitive polyamideimide resin composition M1 (Example 1) showed low sensitivity in i-line exposure but sufficient sensitivity and resolution in g-line exposure (436 nm).

  Table 3 shows the shrinkage of the film when the film (pre-baked film) of the positive photosensitive polyamideimide resin composition of the present invention was heat-treated (cured). Resin compositions M1 to M9 (Examples 1 to 9) all exhibited a low shrinkage of about 10%. On the other hand, in the film (Comparative Example 1) of the positive photosensitive resin composition M10 using polyamide (protector of the polybenzoxazole precursor) instead of polyamideimide, water is eliminated due to a ring-closing reaction during curing. Therefore, the shrinkage rate was high and was 20% or more.

  Table 3 shows the physical properties of the positive photosensitive polyamideimide resin cured film. The positive photosensitive polyamideimide resin compositions M1 to M9 of the present invention showed Tg of about 220 ° C. even when cured at 200 ° C., and EL showed 10% or more. In particular, Tg and EL of the resin composition M9 (Example 9) containing a small amount of a crosslinking agent showed high values. In Example 2, 175 ° C. microwave curing (curing condition ii) showed sufficient Tg and EL comparable to a film cured by 200 ° C. heat curing (curing condition i). On the other hand, the cured film (Comparative Example 1) of the positive photosensitive resin composition M10 using polyamide (protector of the polybenzoxazole precursor) does not have sufficient dehydration ring closure reaction at a relatively low curing temperature of 200 ° C. Since it was not brittle, EL was 10% or less. Furthermore, since the film was broken during the measurement, Tg could not be measured by TMA.

  As described above, the positive photosensitive polyamideimide resin composition, the pattern production method, and the electronic component according to the present invention can be exposed with i-line and developed with an aqueous alkali (TMAH) solution. Accordingly, when a positive photosensitive polyamideimide resin composition is used, a pattern having a good shape with excellent sensitivity and resolution can be obtained. Further, the positive photosensitive polyamideimide resin composition according to the present invention is excellent in film physical properties even when cured at 200 ° C. or lower. Therefore, a pattern having a good shape with excellent physical properties such as heat resistance can be obtained. Furthermore, since the process can be performed at a low temperature, defects due to heat of the device can be reduced, which is useful for electronic parts such as semiconductor devices having excellent reliability. On the other hand, the positive photosensitive polyamideimide resin composition according to the present invention has high dimensional stability because of its small volume shrinkage at the time of curing, and in this respect also, it is useful for electronic parts such as semiconductor devices having excellent reliability.

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. It is a schematic sectional drawing which shows the example of the other electronic component of this invention. It is a schematic sectional drawing which shows the example of the other electronic component of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Semiconductor substrate 2 Protective film 3 1st conductor layer 4 Interlayer insulating film layer 5 Photosensitive resin layer 6A, 6B, 6C, 6D Window 7 2nd conductor layer 8 Surface protective film layer 11 Interlayer insulating layer 12 Al wiring layer 13 Insulating layer 14 Surface protective film layer 15 Pad portion 16 Rewiring layer 17 Conductive ball 18 Core 19 Cover coat layer 20 Barrier metal 21 Color 22 Underfill 23 Silicon chip 24 Connection portion

Claims (12)

A positive electrode comprising (A) a polyamideimide having a repeating unit represented by the following general formula (I), (B) a compound capable of generating an acid upon irradiation with radiation, and (C) a solvent. Type photosensitive polyamide-imide resin composition.

(In the formula, m is a positive number of 1 or more. In the formula, U represents a (2 + m) -valent organic group having an aromatic ring , V represents a trivalent organic group, and W represents active hydrogen. A divalent organic group which does not have a monovalent acetal or ketal which is bonded to an aromatic ring in U, R is decomposed by the action of an acid and can be converted to a hydrogen atom And a group selected from the group consisting of an alkoxyalkyl group, an alkylsilyl group, an alkoxycarbonyl group, and an alkyl group. U wherein -OR in formula (I) is bonded, positive photosensitive polyamideimide resin composition according to claim 1, characterized in that the organic group represented by the following general formula (II) .

(In the formula, m ′ is a positive number of 1 or more, n ′ is a positive number of 1 to 1,000, and U ′ represents a (2 + m) -valent organic group having an aromatic ring. , G represents a tetravalent organic group, a group represented by -OR is bonded to an aromatic ring in U ', and R is a monovalent acetal which can be decomposed and converted into a hydrogen atom by the action of an acid, or A group selected from the group consisting of a group constituting an ketal, an alkoxyalkyl group, an alkylsilyl group, an alkoxycarbonyl group and an alkyl group.)   3. The positive photosensitive polyamideimide resin composition according to claim 1, wherein V in the general formula (I) is an organic group having a substituted or unsubstituted cyclic structure.   4. The component according to claim 1, wherein 0.01 to 50 parts by weight of the component (B) are blended with 100 parts by weight of the component (A). 5. A positive photosensitive polyamide-imide resin composition.   The positive photosensitive polyamide according to any one of claims 1 to 4, wherein the component (B) is an aromatic N-oxyimide sulfonate, an onium salt, or an oxime ester. Imide resin composition.   6. The positive photosensitive resin as claimed in claim 1, further comprising (D) a compound having an organic group that can be converted into a carboxylic acid or a phenolic hydroxyl group by acid catalysis. -Based polyamideimide resin composition.   The component (D) is a compound having a group represented by —COOQ in the molecule (where Q represents a monovalent organic group that can be decomposed by the action of an acid and converted into a hydrogen atom). The positive photosensitive polyamide-imide resin composition according to claim 6.   The positive photosensitive polyamideimide resin composition according to claim 6 or 7, wherein the component (D) is contained in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the component (A).   A process of applying the positive photosensitive polyamideimide resin composition according to any one of claims 1 to 8 on a support substrate and drying the photosensitive resin film obtained by the drying process. A method for producing a pattern, comprising a step of exposing, a step of developing the photosensitive resin film after the exposure using an alkaline aqueous solution, and a step of heat-treating the photosensitive resin film after the development.   The pattern manufacturing method according to claim 9, further comprising a heating step after the exposure step.   The method for producing a pattern according to claim 9 or 10, wherein, in the step of heat-treating the photosensitive resin film after development, a heating temperature is 200 ° C or lower.   It is an electronic component which has an electronic device which has a layer of a pattern obtained by a manufacturing method of a pattern given in any 1 paragraph among Claims 9-11, and in said electronic device, said pattern of said pattern An electronic component comprising the layer as an interlayer insulating film layer or a surface protective film layer.

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