JP5736993B2 - Photosensitive resin composition, method for producing patterned cured film, and electronic component - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a method for producing a cured pattern film using the resin composition, an interlayer insulating film, a surface protective film, and an electronic component, and in particular, adhesion and heat resistance under high temperature and high humidity conditions. The present invention also relates to a photosensitive resin composition excellent in chemical resistance and capable of obtaining a pattern having a good shape, a method for producing a patterned cured film using the resin composition, an interlayer insulating film, a surface protective film, and an electronic component.

  Conventionally, polyimide having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like has been used for a surface protective film and an interlayer insulating film of a semiconductor element. In recent years, a photosensitive polyimide having a photosensitive property imparted to the polyimide itself has been used, and when this is used, the pattern production process can be simplified and a complicated production process can be shortened.

  As the photosensitive polyimide, an organic solvent such as N-methylpyrrolidone has been used for development. Recently, in consideration of the environment, a positive photosensitive polyimide that can be developed with an aqueous alkaline solution has been proposed. . As a positive photosensitive polyimide, a method of mixing a naphthoquinonediazide compound as a photosensitive agent with polyimide or a polyimide precursor (for example, see Patent Documents 1 and 2) has been proposed.

  Recently, a polybenzoxazole or a polybenzoxazole precursor has been proposed as a positive photosensitive resin that can be developed with an alkaline aqueous solution. Since polybenzoxazole or polybenzoxazole precursor has a larger contrast between the dissolution rate of the exposed portion and the unexposed portion than polyimide or polyimide precursor, it is possible to form a more precise pattern (for example, patent Reference 3 and Non-Patent Document 1).

JP-A 64-60630 US Pat. No. 4,395,482 JP 2009-265520 A

J. et al. Photopolym. Sci. Technol. , Vol. 17, 207-213.

Recently, semiconductor devices have been highly integrated and miniaturized, and there is a demand for thinning and miniaturization of package substrates. Therefore, in order to suppress damage to the substrate and the like, a manufacturing process at a low temperature is desired when the interlayer insulating film and the surface protective film of such a semiconductor element are formed.
However, the polybenzoxazole precursor described in Non-Patent Document 1 needs to be dehydrated and closed at a high temperature in a heat treatment step when producing a patterned cured film. And when the photosensitive resin composition containing this polybenzoxazole precursor was dehydrated and closed at a low temperature of 250 ° C. or lower, the characteristics of the pattern cured film such as chemical resistance and adhesion to the substrate tended to deteriorate. . In particular, with the diversification of applications of semiconductor elements, interlayer insulating films and surface protective films using photosensitive resin compositions are required to adhere to a substrate under high temperature and high humidity conditions. In this dehydration ring closure, it was difficult to provide sufficient adhesion to the substrate under high temperature and high humidity conditions.

An object of the present invention is to provide a photosensitive film that exhibits a high dehydration ring closure rate even when heat treatment is performed at 250 ° C. or less, and provides a cured pattern film having excellent chemical resistance and adhesion to a substrate under high temperature and high humidity conditions. It is providing a functional resin composition.
Moreover, this invention provides the manufacturing method of the pattern cured film using the said photosensitive resin composition. Furthermore, an object of the present invention is to provide a highly reliable electronic component by having an interlayer insulating film or a surface protective film using the patterned cured film.

According to the present invention, the following photosensitive resin composition is provided.
That is, the photosensitive resin composition according to the present invention comprises (a) an alkali-soluble resin, (b) a photosensitive agent, (c) a solvent, (d) a cross-linking agent, and (e) a phosphate group, phosphone in the molecule. A compound having an acid group or a phosphinic acid group and having at least one hydroxyl group on the phosphorus atom of these groups is contained.

（式中、Ｕは２価の有機基、単結合、−Ｏ−、又は、−ＳＯ_２−であり、Ｖは２価の有機基を示し、少なくとも、Ｖが炭素数１〜３０の脂肪族構造を含む基であるか、又はＵが主鎖を構成する炭素数が２〜３０の脂肪族構造を含む基である。） In the photosensitive resin composition according to the present invention, the component (a) preferably has any structure of polyimide, polyamic acid, polybenzoxazole, or polyhydroxyamide.
Furthermore, it is more preferable that the component (a) has a structural unit represented by the general formula (I).

(In the formula, U represents a divalent organic group, a single bond, —O—, or —SO ₂ —, V represents a divalent organic group, and at least V is an aliphatic group having 1 to 30 carbon atoms. It is a group containing a structure, or U is a group containing an aliphatic structure having 2 to 30 carbon atoms constituting the main chain.)

（式中、Ｒ^２１、Ｒ^２２、Ｒ^２３及びＲ^２４は各々独立に、１価の有機基である。） In the photosensitive resin composition according to the present invention, the component (e) is preferably a compound represented by any one of the following general formulas (II) to (V).

(Wherein R ²¹ , R ²² , R ²³ and R ²⁴ are each independently a monovalent organic group.)

（式中、Ｒ^５及びＲ^８は各々独立にアクリロイル基（ＣＨ_２＝ＣＨＣＯ−）又はメタアクリロイル基（ＣＨ_２＝Ｃ（ＣＨ_３）ＣＯ−）を示し、Ｒ^６及びＲ^７は各々独立に水素原子又はメチル基を示す。ｔ、ｕ、ｖ、ｗ、ｘ、及びｙは各々独立に１〜８の整数を示す。） In the photosensitive resin composition according to the present invention, the component (e) has a vinyl group, an acryloyl group, a methacryloyl group, a phenyl group, a hydroxyphenyl group, an amino group, or a dialkylamino group having 1 to 8 carbon atoms in the molecule. And a compound having either an alkylamino group having 1 to 8 carbon atoms or an alkyl group having 1 to 15 carbon atoms.
Furthermore, the component (e) is more preferably a compound represented by any of the following formulas (VI) to (VIII).

(Wherein R ⁵ and R ⁸ each independently represents an acryloyl group (CH ₂ ═CHCO—) or a methacryloyl group (CH ₂ ═C (CH ₃ ) CO—), and R ⁶ and R ⁷ each independently represent A hydrogen atom or a methyl group, t, u, v, w, x, and y each independently represent an integer of 1 to 8)

  In the photosensitive resin composition according to the present invention, the component (d) is preferably a compound having a methylol group or an alkoxyalkyl group.

  In the photosensitive resin composition according to the present invention, the component (b) is preferably a compound that generates an acid or a radical by light.

  Moreover, the method for producing a cured pattern film according to the present invention includes a step of applying and drying the photosensitive resin composition on a support substrate to form a photosensitive resin film, and a photosensitive resin obtained by the application and drying steps. It includes a step of exposing the film to a predetermined pattern, a step of developing the exposed photosensitive resin film using an alkaline aqueous solution, and a step of heat-treating the developed photosensitive resin film.

  In the method for producing a patterned cured film according to the present invention, in the step of heat-treating the photosensitive resin film after development, the heat treatment temperature is preferably 250 ° C. or lower, more preferably 200 ° C. or lower. preferable.

  The interlayer insulating film or the surface protective film of the present invention can be obtained by the method for producing a patterned cured film. The electronic component of the present invention has the interlayer insulating film or the surface protective film.

By using the photosensitive resin composition of the present invention, even when heat treatment is performed at 250 ° C. or less, a high dehydration ring closure rate is exhibited, and excellent chemical resistance and adhesion to a substrate under high temperature and high humidity conditions are exhibited. It is possible to form a patterned cured film. In addition, the photosensitive resin composition of the present invention has sufficient sensitivity and mechanical properties that are comparable to those heat-treated at a high temperature even when heat-treated at 250 ° C. or lower.
Furthermore, the photosensitive resin composition of the present invention can form a cured pattern film having chemical resistance and adhesion to a substrate under high temperature and high humidity even when heat treatment is performed at 200 ° C. or lower. is there.

  Moreover, according to the manufacturing method of the pattern cured film of this invention, the pattern cured film excellent in adhesiveness can be obtained by use of the said photosensitive resin composition. Furthermore, the present invention can provide an electronic component with high reliability by having an interlayer insulating film and a surface protective film using the patterned cured film.

It is a schematic sectional drawing of the semiconductor device which has the rewiring structure which is embodiment of this invention.

  Below, the photosensitive resin composition by this invention, the manufacturing method of the pattern cured film using this resin composition, and embodiment of an electronic component are described in detail. The present invention is not limited to the following embodiments.

[Photosensitive resin composition]
First, the photosensitive resin composition according to the present invention will be described.
The photosensitive resin composition of the present invention comprises (a) an alkali-soluble resin, (b) a photosensitizer, (c) a solvent, (d) a cross-linking agent, and (e) a phosphate group or phosphonic acid in the molecule. A compound having a group or a phosphinic acid group and having at least one hydroxyl group on the phosphorus atom of these groups.
In the description of the present specification, in some cases, they are simply referred to as (a) component, (b) component, (c) component, (d) component, and (e) component, respectively. Hereinafter, each component will be described.

((A) component: alkali-soluble resin)
The component (a) (alkali-soluble resin) in the present invention is a resin that is soluble in an alkaline solution such as a tetramethylammonium hydroxide aqueous solution, a metal hydroxide aqueous solution, or an organic amine aqueous solution. In general, since an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by weight is used, the component (a) is preferably soluble in this aqueous solution.

  Here, one standard that the photosensitive resin composition of the present invention is soluble in an alkaline solution will be described below. (A) Component alone and an arbitrary solvent, or a resin solution obtained from component (b), component (c), component (d) and component (e) described below in order A resin film having a thickness of about 5 μm is formed by spin coating. This is immersed in any one of tetramethylammonium hydroxide aqueous solution, metal hydroxide aqueous solution, and organic amine aqueous solution at 20-25 ° C. As a result, when it can be dissolved as a uniform solution, it is determined that the component (a) used is soluble in an alkaline aqueous solution.

As the component (a), it is preferable to use polyimide, polyamic acid (polyimide precursor), polybenzoxazole, or polyhydroxyamide (polybenzoxazole precursor) from the viewpoint of excellent heat resistance. Further, from the viewpoint of solubility in an alkaline aqueous solution, a compound having a phenolic hydroxyl group, a carboxyl group, or a sulfonic acid group in the molecule is preferable.
Furthermore, from the viewpoint of achieving both heat resistance (evaluable by glass transition temperature (Tg) and the like) and solubility in an alkaline solution, polyamic acid, polyhydroxyamide, polyimide having a phenolic hydroxyl group, or carboxyl group is added. It is more preferable to use the polyimide which has. In addition, it is particularly preferable to use polyhydroxyamide from the viewpoint of better heat resistance and solubility in an aqueous alkali solution.

（式中、Ｕは２価の有機基、単結合、−Ｏ−、又は、−ＳＯ_２−であり、Ｖは２価の有機基を示し、少なくとも、Ｖが炭素数１〜３０の脂肪族構造を含む基であるか、又はＵが、主鎖を構成する炭素数が２〜３０の脂肪族構造を含む基であることが好ましい。）
尚、主鎖の部分を構成する炭素とは、２つのベンゼン環をつなぐ直鎖（分岐は含まない）を構成する炭素を意味する。
Ｖが炭素数１〜３０の脂肪族構造を含む基であるとき、Ｕは任意の２価の有機基でよく、Ｕが、主鎖を構成する炭素数が２〜３０の脂肪族構造を含む基であるとき、Ｖは任意の２価の有機基でよく、Ｖが炭素数１〜３０の脂肪族構造を含む基であり、かつ、Ｕが主鎖の部分を構成する炭素数が２〜３０の脂肪族構造を含む基であってもよい。
尚、一般式（Ｉ）で表される構造単位における、同一のベンゼン環上に結合しているヒドロキシ基とアミド基は、加熱工程における脱水閉環により、耐熱性、機械特性及び電気特性に優れるオキサゾール環に変換される。 From the viewpoint of exhibiting good mechanical properties (evaluable by measuring elongation at break) and heat resistance (evaluable by measuring glass transition temperature (Tg), etc.), the component (a) is represented by the following general formula (I). A compound having a structural unit is preferred.

(In the formula, U represents a divalent organic group, a single bond, —O—, or —SO ₂ —, V represents a divalent organic group, and at least V is an aliphatic group having 1 to 30 carbon atoms. It is preferably a group containing a structure, or U is a group containing an aliphatic structure having 2 to 30 carbon atoms constituting the main chain.)
The carbon constituting the main chain portion means carbon constituting a straight chain (not including a branch) connecting two benzene rings.
When V is a group including an aliphatic structure having 1 to 30 carbon atoms, U may be any divalent organic group, and U includes an aliphatic structure having 2 to 30 carbon atoms constituting the main chain. When it is a group, V may be any divalent organic group, V is a group containing an aliphatic structure having 1 to 30 carbon atoms, and U has 2 to 2 carbon atoms constituting the main chain portion. It may be a group containing 30 aliphatic structures.
In addition, in the structural unit represented by the general formula (I), the hydroxy group and the amide group bonded on the same benzene ring are oxazole having excellent heat resistance, mechanical properties, and electrical properties by dehydration ring closure in the heating step. Converted to a ring.

（式中、Ｒ^９及びＲ^１０は各々独立に水素、フッ素又は炭素数１〜６のアルキル基であり、Ｕは２価の有機基、単結合、−Ｏ−、又は、−ＳＯ_２−であり、ｎは１〜３０の整数である。）
さらに、一般式（IX）で表される構造単位を有する化合物において、ｎは７〜３０の整数であることが好ましい。ｎが７〜３０の整数であると、パターン硬化膜の弾性率が低く、破断伸びが良好である。また、ｎが７〜３０の整数であると、感光性樹脂組成物がＮ−メチル−２−ピロリドン、γ−ブチロラクトン、プロピレングリコールモノメチルエーテルアセテート等の溶媒に容易に溶け、保存安定性が向上する。 In addition, since the dehydration ring closure rate is high in the heating step at 250 ° C. or lower, and exhibits good heat resistance, mechanical strength, and high transparency in the ultraviolet and visible light regions, the component (a) is represented by the general formula (IX). It is preferable that the compound has a structural unit.

(Wherein R ⁹ and R ¹⁰ are each independently hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms, U is a divalent organic group, a single bond, —O—, or —SO ₂ —. And n is an integer from 1 to 30.)
Furthermore, in the compound having the structural unit represented by the general formula (IX), n is preferably an integer of 7 to 30. When n is an integer of 7 to 30, the elastic modulus of the pattern cured film is low and the elongation at break is good. Further, when n is an integer of 7 to 30, the photosensitive resin composition is easily dissolved in a solvent such as N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monomethyl ether acetate, and storage stability is improved. .

  A polybenzoxazole precursor having a structural unit represented by the general formula (I) or (IX) generally comprises a dicarboxylic acid or a dicarboxylic acid derivative (hereinafter referred to as a dicarboxylic acid) and a diamine having a dihydroxy group. And can be synthesized by a synthesis method described later. In general formula (I) or (IX), U is a group of a residue of diamines, and V is a residue of dicarboxylic acids.

In the general formulas (I) and (IX), examples of diamines that give a divalent organic group represented by U, a single bond, —O—, or —SO ₂ — include 3,3′-diamino-4, 4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 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, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (4-amino-3-hydroxyphenyl) propane and the like, these The present invention is not limited. These diamines can be used alone or in combination of two or more.

（式中、ｍは１〜６の整数である。） In the general formulas (I) and (IX), when U is a group containing an aliphatic structure having 2 to 30 carbon atoms constituting the main chain, the diamine that gives such a polybenzoxazole precursor includes carbon. Diamines containing an aliphatic structure having a number of 2 to 30 are used. For example, the compound shown with the following general formula is mentioned.

(In the formula, m is an integer of 1 to 6.)

  In the general formula (I), examples of the dicarboxylic acid that gives a divalent organic group represented by V include isophthalic acid, terephthalic acid, and 2,2-bis (4-carboxyphenyl) -1,1,1,3. 3,3-hexafluoropropane, 4,4′-dicarboxybiphenyl, 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2- Bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid and the like can be mentioned. It is not limited. These compounds can be used alone or in combination of two or more.

  When V in the general formula (I) is a group containing an aliphatic structure having 1 to 30 carbon atoms, examples of the dicarboxylic acid that gives such a polybenzoxazole precursor include malonic acid, dimethylmalonic acid, ethylmalonic acid, Isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid , Hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipine Acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid Dodecanafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecane Diacid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosandioic acid, triacontane diacid Examples include acid entriacontanedioic acid, dotriacontanedioic acid, and diglycolic acid.

（式中Ｚはそれぞれ炭素数１〜６の炭化水素基、ｎは１〜６の整数である。） Furthermore, the dicarboxylic acid etc. which are shown with the following general formula are mentioned.

(Wherein Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6)

  Even when the component (a) has a structural unit represented by the general formula (IX), these compounds can be used as dicarboxylic acids.

（式中、Ｕ及びＷは各々独立に２価の有機基、単結合、−Ｏ−、又は、−ＳＯ_２−であり、Ｖ及びＸは各々独立に２価の有機基を示す。Ｕ及びＶについて、少なくとも、Ｖが炭素数１〜３０の脂肪族構造を含む基であるか、又はＵが主鎖を構成する炭素数が２〜３０の脂肪族構造を含む基である。構造単位Ａが一般式（Ｉ）で示される構造単位部分である。ｊ及びｋは構造単位Ａと構造単位Ｂのモル分率を示し、ｊ及びｋの和は１００モル％である。）
ここで、式中のｊ及びｋのモル分率は、ｊ＝５〜８５モル％、ｋ＝１５〜９５モル％であることがパターン性、機械特性、耐熱性及び耐薬品性の観点で好ましい。
尚、一般式（Ｘ）で表されるヒドロキシ基を含有するアミン類の残基は、加熱工程における脱水閉環により、機械特性、耐熱性及び電気特性に優れるオキサゾールに変換される。
尚、共重合体は、ブロック共重合体でもランダム共重合体でもよい。式（Ｘ）は共重合体の構成単位及び構造単位間の結合を示したものであり、ブロック共重合体を記載したものではない。後述する式（XI）又は（XII）についても同様である。 As the polybenzoxazole precursor having the structural unit represented by the general formula (I), a polybenzoxazole precursor having a structural unit represented by the following general formula (X) which is a copolymer may be used. it can.

(In the formula, U and W are each independently a divalent organic group, a single bond, —O—, or —SO ₂ —, and V and X each independently represent a divalent organic group. U and Regarding V, at least V is a group including an aliphatic structure having 1 to 30 carbon atoms, or U is a group including an aliphatic structure having 2 to 30 carbon atoms constituting the main chain. Is the structural unit portion represented by the general formula (I), j and k represent the mole fraction of the structural unit A and the structural unit B, and the sum of j and k is 100 mol%.)
Here, the molar fractions of j and k in the formula are preferably j = 5 to 85 mol% and k = 15 to 95 mol% from the viewpoints of patternability, mechanical properties, heat resistance and chemical resistance. .
In addition, the residue of amines containing the hydroxy group represented by the general formula (X) is converted into oxazole having excellent mechanical properties, heat resistance and electrical properties by dehydration ring closure in the heating step.
The copolymer may be a block copolymer or a random copolymer. Formula (X) shows the bonds between the structural units and structural units of the copolymer, and does not describe a block copolymer. The same applies to formula (XI) or (XII) described later.

Moreover, the polybenzoxazole precursor which has a structural unit shown by the following general formula (XI) or (XII) should be used as a polybenzoxazole precursor which has a structural unit represented by general formula (I). You can also.
The structural unit represented by the general formula (XI) or (XII) is a polybenzoxazole structural unit other than the structural unit represented by the general formula (I), a polyimide or a polyimide precursor (polyamic acid, polyamic acid ester, etc.). Has structural units and the like.

（式中、Ｕ及びＹは各々独立に２価の有機基、単結合、−Ｏ−、又は、−ＳＯ_２−であり、Ｖ及びＺは各々独立に２価の有機基を示す。Ｕ及びＶについて、少なくともＶが炭素数１〜３０の脂肪族構造を含む基であるか、又はＵが主鎖を構成する炭素数が２〜３０の脂肪族構造を含む基である。ｊ及びｌは、それぞれの構造単位のモル分率を示し、ｊ及びｌの和は１００モル％であり、ｊが６０〜９９．９モル％、ｌが０．１〜４０モル％である。）
ここで、アルカリ水溶液に対する可溶性は、式中、ベンゼン環に結合するヒドロキシル基（一般にはフェノール性水酸基）に依存するため、式中のｊとｌのモル分率は、ｊ＝８０〜９９．９モル％、ｌ＝０．１〜２０モル％であることが好ましい。

(In the formula, U and Y are each independently a divalent organic group, a single bond, —O—, or —SO ₂ —, and V and Z each independently represent a divalent organic group. U and With respect to V, at least V is a group containing an aliphatic structure having 1 to 30 carbon atoms, or U is a group containing an aliphatic structure having 2 to 30 carbon atoms constituting the main chain, j and l And the sum of j and l is 100 mol%, j is 60 to 99.9 mol%, and l is 0.1 to 40 mol%.
Here, since solubility in an aqueous alkali solution depends on a hydroxyl group (generally a phenolic hydroxyl group) bonded to the benzene ring in the formula, the molar fraction of j and l in the formula is j = 80 to 99.9. It is preferable that they are mol% and l = 0.1-20 mol%.

（式中、Ｕ、Ｗ及びＹは各々独立に２価の有機基、単結合、−Ｏ−、又は、−ＳＯ_２−であり、Ｖ、Ｘ及びＺは各々独立に２価の有機基を示す。Ｕ及びＶについて、少なくとも、Ｖが炭素数１〜３０の脂肪族構造を含む基であるか、又はＵが主鎖を構成する炭素数が２〜３０の脂肪族構造を含む基である。ｊ、ｋ及びｌは、それぞれの構造単位のモル分率を示し、ｊ、ｋ及びｌの和は１００モル％であり、ｊ及びｋの和：ｊ＋ｋが６０〜９９．９モル％、ｌが０．１〜４０モル％である。）
ここで、アルカリ水溶液に対する可溶性は、式中、ベンゼン環に結合するヒドロキシル基（一般にはフェノール性水酸基）に依存する。よってアルカリ水溶液に対する可溶性という観点から、式中のｊ、ｋ及びｌのモル分率は、ｊ＋ｋ＝８０〜９９．９モル％、ｌ＝０．１〜２０モル％であることがより好ましい。尚、上記一般式（XI）及び（XII）において、Ｙは、Ｕ及びＷとは異なるものであり、一般には、フェノール性水酸基を含まないジアミン類の残基である。

Wherein U, W and Y are each independently a divalent organic group, a single bond, —O— or —SO ₂ —, and V, X and Z are each independently a divalent organic group. As for U and V, at least V is a group containing an aliphatic structure having 1 to 30 carbon atoms, or U is a group containing an aliphatic structure having 2 to 30 carbon atoms constituting the main chain. J, k, and l represent the mole fraction of each structural unit, and the sum of j, k, and l is 100 mol%, and the sum of j and k: j + k is 60 to 99.9 mol%, l Is 0.1 to 40 mol%.)
Here, the solubility in an alkaline aqueous solution depends on the hydroxyl group (generally a phenolic hydroxyl group) bonded to the benzene ring in the formula. Therefore, from the viewpoint of solubility in an aqueous alkali solution, the molar fractions of j, k and l in the formula are more preferably j + k = 80 to 99.9 mol% and l = 0.1 to 20 mol%. In the above general formulas (XI) and (XII), Y is different from U and W, and is generally a residue of a diamine that does not contain a phenolic hydroxyl group.

In the general formulas (XI) and (XII), the divalent organic group represented by U and W, a single bond, —O—, or —SO ₂ — is the U in the general formulas (I) and (IX). The divalent organic group represented by V, X, and Z is a residue of the diamine described above as a diamine that gives a divalent organic group, a single bond, —O—, or —SO ₂ —. These are residues of the dicarboxylic acids described above as the dicarboxylic acids that give the group represented by V in the general formula (I). Y is preferably a divalent aromatic group or aliphatic group, preferably has 4 to 40 carbon atoms, and more preferably is an aromatic group having 4 to 40 carbon atoms.

  Examples of the diamine that gives the divalent organic group represented by Y in the general formulas (XI) and (XII) include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, and 4,4′-diaminodiphenyl. Sulfone, 4,4′-diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3 -Aromatic diamine compounds such as aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenoxy) benzene It is done. Further, as a diamine compound having a silicone group, “LP-7100”, “X-22-161AS”, “X-22-161A”, “X-22-161B”, “X-22-161C” and “X” -22-161E "(both manufactured by Shin-Etsu Chemical Co., Ltd., trade name). Diamines that give a divalent organic group represented by Y are not limited to these. These compounds are used alone or in combination of two or more.

  The molecular weight of the component (a) is preferably 3,000 to 200,000 in terms of weight average molecular weight, more preferably 5,000 to 100,000, and still more preferably 10,000 to 50,000. 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 the present invention, (a) the method for producing the alkali-soluble resin is not particularly limited. For example, the polyhydroxyamide having the structural unit represented by the general formulas (I) and (IX) is generally a dicarboxylic acid and a hydroxy group. It can be synthesized from diamines having a group.
Specifically, it can be synthesized by converting a dicarboxylic acid into a dihalide derivative and then reacting with a diamine. As the dihalide derivative, a dichloride derivative is preferable.

As a method of synthesizing a dichloride derivative, it can be synthesized by reacting a dicarboxylic acid and a halogenating agent in a solvent or reacting in an excess halogenating agent and then distilling off the excess. As the halogenating agent, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride, etc., which are used in the usual acid chlorideation reaction of carboxylic acid can be used.
As the reaction solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, benzene and the like can be used.

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

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

  Polyamic acid can generally be synthesized by reacting tetracarboxylic dianhydride or its derivative with diamines in an organic solvent. As an organic solvent, the thing similar to the thing used for the synthesis | combination of the said polyhydroxyamide can be used.

  Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride. Anhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl Ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,5 6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6- Pyridine tetracar Acid dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4 ′ -Aromatic tetracarboxylic dianhydrides such as tetraphenylsilane tetracarboxylic dianhydride and 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride. It can be used alone or in combination of two or more.

  Examples of diamines include aromatic diamines, aliphatic diamines, and alicyclic diamines. Specifically, 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,5-diaminoterephthalic acid, bis (4-amino-3-carboxyphenyl) methylene, Bis (4-amino-3-carboxyphenyl) ether, 4,4-diamino-3,3′-dicarboxybiphenyl, 4,4′-diamino-5,5′-dicarboxy-2,2′-dimethylbiphenyl 1,3-diamino-4-hydroxybenzene, 1,3-diamino-5-hydroxybenzene, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′- Dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4) Hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) ether, bis (4-amino-3-hydroxyphenyl) ether, bis (3-amino- 4-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 1,4-diaminocyclohexane, 1,1,3,3-tetramethyl 1,3-bis (4- Aminophenyl) disiloxane, poly (propylene glycol) diamine, and the like, and these can be used alone or in combination of two or more.

((B) component: photosensitive agent)
The photosensitive resin composition of this invention contains the (b) photosensitive agent with the said polybenzoxazole precursor. This photosensitive agent is a resin composition that is coated on a substrate, and when the photosensitive resin film formed is irradiated with light, it reacts with the light and dissolves in the developer in the irradiated and unirradiated areas. It has a function to give a difference to. Although there is no restriction | limiting in particular in the photosensitive agent used as (b) component by this invention, It is preferable that it generate | occur | produces an acid or a radical by light.

  When using the photosensitive resin composition of this invention as a positive photosensitive resin composition, it is more preferable that (b) photosensitive agent is what generate | occur | produces an acid by light (photo acid generator). The photoacid generator has a function of generating an acid by light irradiation and increasing the solubility of the light irradiation portion in an alkaline aqueous solution. Examples of such a photoacid generator include an o-quinonediazide compound, an aryldiazonium salt, a diaryliodonium salt, a triarylsulfonium salt, and the like, and it is preferable to use an o-quinonediazide compound from the viewpoint of developing good sensitivity. .

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

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

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

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

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

In the general formulas (I), (X), (XI) and (XII), the structure represented by V, X, Y and Z is a group having a photocrosslinkable group such as an acryloyl group or a methacryloyl group. In some cases, it is preferable to use a component (photopolymerization initiator) that generates radicals as the component (b) (photosensitive agent). When a photopolymerization initiator is used as the component (b), the photosensitive resin composition of the present invention can be used as a negative photosensitive resin composition.
As such a photopolymerization initiator, known compounds can be used as long as they are compounds that generate radicals upon irradiation with light in addition to peroxides and azo compounds. Examples of such a compound include 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy)- Phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2 -Methyl-propan-1-one, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] ethyl ester, phenylglyoxylic acid methyl ester, 2-dimethylamino-2- (4- Methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-ethylhex Silu 4-dimethylaminobenzoate, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy- Aromatic ketones such as cyclohexyl-phenyl-ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone-1,2,4-diethylthioxanthone, 2-ethylanthraquinone, phenanthrenequinone, benzyl Benzyl derivatives such as dimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2 -(O-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o Methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer 2,4,5-triarylimidazole dimer such as 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,7-bis (9 , 9'-acridinyl) heptane, acridine derivatives, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6, -trimethylbenzoyl) -phenylphosphine Examples thereof include bisacylphosphine oxides such as fin oxides and compounds having maleimide. These can be used alone or in combination of two or more.
In this negative photosensitive resin composition, the component (b) has a function of reducing the solubility of the irradiated portion in an alkaline aqueous solution by a crosslinking reaction by light irradiation.

  In the photosensitive resin composition of the present invention, the content of the component (b) (photosensitive agent) is the component (a) (polybenzoxazole precursor) in terms of the difference in dissolution rate and sensitivity between the exposed and unexposed areas. 5-100 mass parts is preferable with respect to 100 mass parts, and 8-40 mass parts is more preferable.

((C) component: solvent)
As the component (c) (solvent) used in the present invention, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, methyl amyl ketone In general, there is no particular limitation as long as it can sufficiently dissolve other components in the photosensitive resin composition.
Among these, from the viewpoint of excellent solubility of each component and coating property at the time of resin film formation, γ-butyrolactone, ethyl lactate, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, N, N-dimethylformamide, N, It is preferable to use N-dimethylacetamide.

  These solvents can be used alone or in combination of two or more. Further, the amount of the solvent to be used is not particularly limited, but it is generally preferably adjusted so that the ratio of the solvent in the photosensitive resin composition is 20 to 90% by mass.

((D) component: crosslinking agent)
The component (d) (crosslinking agent) used in the present invention reacts with the polybenzoxazole precursor or polybenzoxazole (crosslinking reaction) in the step of heat treatment after application, exposure and development of the photosensitive resin composition, Alternatively, the crosslinking agent itself is polymerized. Thereby, even when the photosensitive resin composition is cured at a relatively low temperature, for example, 200 ° C. or less, good mechanical properties, chemical resistance and flux resistance can be imparted.

The component (d) is not particularly limited as long as it is a compound that crosslinks or polymerizes in the heat treatment step, but an alkoxyalkyl group such as a methylol group, an alkoxymethyl group, an epoxy group, an oxetanyl group, or a vinyl ether group is contained in the molecule. It is preferable that it is a compound having.
A compound in which these groups are bonded to a benzene ring, a melamine resin or a urea resin in which the N-position is substituted with a methylol group or an alkoxymethyl group are preferable. In addition, a compound in which these groups are bonded to a benzene ring having a phenolic hydroxyl group is more preferable in that the sensitivity can be improved by increasing the dissolution rate of the exposed area during development. Above all, from the viewpoint of good sensitivity and varnish stability, and prevention of melting of the photosensitive resin film upon curing of the photosensitive resin film after pattern formation, two or more methylol groups or alkoxy in the molecule A compound having a methyl group is more preferred.

（式中、Ｘは単結合、−Ｏ−、−ＳＯ_２−又は１〜４価の有機基を示し、Ｒ^１１は水素原子又は一価の有機基を示し、Ｒ^１２は一価の有機基を示す。ｎは１〜４の整数であり、ｐは１〜４の整数であり、ｑは０〜３の整数である。）

（式中、Ｙは各々独立に水素原子、炭素原子数１〜１０のアルキル基、その水素原子の一部又は全部がフッ素原子で置換されたフルオロアルキル基、その水素原子の一部がヒドロキシル基で置換されたヒドロキシアルキル基、又は、炭素原子数１〜１０のアルコキシ基であり、Ｒ^１３及びＲ^１４は各々独立に一価の有機基を示し、Ｒ^１５及びＲ^１６は各々独立に水素原子又は一価の有機基を示し、ｒ及びｔは各々独立に１〜３の整数であり、ｓ及びｕは各々独立に０〜３の整数である）

（式中、Ｒ^１７及びＲ^１８は各々独立に水素原子又は一価の有機基を示し、Ｒ^１８は互いが結合することで環構造となっていてもよい。）

（式中、Ｒ^１９、Ｒ^２０、Ｒ^２１、Ｒ^２２、Ｒ^２３及びＲ^２４は各々独立に水素原子、メチロール基又はアルコキシメチル基を示す。）
尚、一般式（XIII）（XIV）、及び（XV）において、一価の有機基としては、炭素原子数１〜１０の、アルキル基、アルコキシ基、ヒドロキシアルキル基、ヒドロキシアルコキシ基、それらの水素原子の一部又は全部がハロゲン原子で置換されたものが好ましいものとして挙げられる。この中でも一般式（XI）で表される化合物を用いると、感光性樹脂組成物を２００℃以下の低温で硬化した場合に、優れた耐薬品性を有する硬化膜が得られるため、好ましい。 (D) As a crosslinking agent, the compound shown by the following general formula (XIII), (XIV), (XV), and (XVI) is mentioned.

(Wherein X represents a single bond, —O—, —SO ₂ — or a monovalent to tetravalent organic group, R ¹¹ represents a hydrogen atom or a monovalent organic group, and R ¹² represents a monovalent organic group. N is an integer of 1 to 4, p is an integer of 1 to 4, and q is an integer of 0 to 3.)

Wherein Y is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group in which part or all of the hydrogen atoms are substituted with fluorine atoms, and part of the hydrogen atoms are hydroxyl groups. Or an alkoxy group having 1 to 10 carbon atoms, R ¹³ and R ¹⁴ each independently represent a monovalent organic group, and R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom. Or a monovalent organic group, r and t are each independently an integer of 1 to 3, and s and u are each independently an integer of 0 to 3)

(Wherein R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a monovalent organic group, and R ¹⁸ may be bonded to each other to form a ring structure.)

(In the formula, R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom, a methylol group or an alkoxymethyl group.)
In the general formulas (XIII), (XIV), and (XV), the monovalent organic group includes an alkyl group, an alkoxy group, a hydroxyalkyl group, a hydroxyalkoxy group, and hydrogen thereof having 1 to 10 carbon atoms. Those in which some or all of the atoms are substituted with halogen atoms are preferred. Among these, it is preferable to use the compound represented by the general formula (XI) because a cured film having excellent chemical resistance can be obtained when the photosensitive resin composition is cured at a low temperature of 200 ° C. or lower.

Specific examples of the compounds represented by the general formulas (XIII) (XIV), (XV), and (XVI) include the following compounds, but are not limited thereto. Moreover, these compounds can be used individually or in combination of 2 or more types.

Among the above compounds, from the viewpoint of compatibility with the component (a), heat resistance and flux resistance, it is more preferable to use the compounds described below as the component (d).

  In the photosensitive resin composition of the present invention, the content of the component (d) is based on 100 parts by weight of the component (a) from the viewpoint of development time, allowable width of the unexposed portion remaining film ratio, and cured film properties. 1 to 50 parts by mass is preferable. Moreover, it is more preferable that it is 15-50 mass parts from a viewpoint of expressing the favorable chemical resistance and flux tolerance of a cured film at the time of hardening a photosensitive resin composition at 250 degrees C or less, and is 20-50 mass parts. More preferably it is.

((E) component: a compound having a phosphoric acid group, a phosphonic acid group, or a phosphinic acid group in the molecule and having at least one hydroxyl group on the phosphorus atom of these groups)
The component (e) of the present invention (a compound having a phosphoric acid group, a phosphonic acid group, or a phosphinic acid group in the molecule and having at least one hydroxyl group on the phosphorus atom of these groups) is composed of copper and a copper alloy, etc. It has the effect of improving adhesion to metal. Moreover, it has the effect which prevents the corrosion of metals, such as copper and a copper alloy, used for the photosensitive resin composition and wiring and a board | substrate.
Furthermore, it has the effect of reducing the difference in dissolution rate between the case where the photosensitive resin composition is applied to a silicon substrate and the case where it is applied onto another substrate, and the effect of suppressing metal migration. Here, metal migration is a phenomenon in which when a bias (voltage) is applied, metal (for example, copper) ions move between opposing electrodes and reduce and precipitate, resulting in a short-circuit between wires. It is.
These effects are particularly prominent when the photosensitive resin composition is cured at a low temperature (for example, 250 ° C. or lower). That is, the present invention is a polyhydroxyamide (for example, a polyhydroxyamide represented by the general formulas (I) and (IX)), which is an alkali-soluble resin preferably used for curing at a low temperature mentioned in the component (a). In addition, the photosensitive resin composition that can be cured at a low temperature by using it together with the component (e) and sufficiently exhibits film properties such as adhesion and mechanical properties even when cured at a low temperature. Can be obtained.
The compound represented by the general formula (XV), which is the component (d) described above, generally gives excellent chemical resistance, but on the other hand, there is a possibility that the adhesion to the substrate is lowered. However, by combining with the component (e) of the present invention, sufficient adhesion to the substrate can be expressed under high temperature and high humidity conditions while maintaining excellent chemical resistance.

（式中、Ｒ^２１、Ｒ^２２、Ｒ^２３及びＲ^２４は各々独立に、１価の有機基である。） Specific examples of the compound having a phosphoric acid group, a phosphonic acid group, or a phosphinic acid group in the molecule and having at least one hydroxyl group on the phosphorus atom of these groups include general formulas (II) to (V). The compound which has the structure represented by these is mentioned.

(Wherein R ²¹ , R ²² , R ²³ and R ²⁴ are each independently a monovalent organic group.)

Specifically, methylsulfonic acid, vinylphosphonic acid, allylphosphonic acid, (aminomethyl) phosphonic acid, (1-aminoethyl) phosphonic acid, methylenediphosphonic acid, etc., dibutyl phosphate, dioctyl phosphate, diphenyl phosphate 1-aminopropyl phosphoric acid, 1-amino-2-methylpropyl phosphoric acid and the like.
From the viewpoint of compatibility with the components (a) to (d), R ²¹ , R ²² , R ²³ and R ²⁴ are vinyl group, acryloyl group, methacryloyl group, phenyl group, hydroxyphenyl group, amino group, carbon group. A dialkylamino group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, or 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms It is preferable to have any of these alkyl groups.

（式中、Ｒ^５及びＲ^８は各々独立にアクリロイル基（ＣＨ_２＝ＣＨＣＯ−）又はメタアクリロイル基（ＣＨ_２＝Ｃ（ＣＨ_３）ＣＯ−）を示し、Ｒ^６及びＲ^７は各々独立に水素原子又はメチル基を示す。ｔ、ｕ、ｖ、ｗ、ｘ、及びｙは各々独立に１〜８の整数を示す。） In addition, from the viewpoint of self-polymerization during curing (for example, polymerization reaction between vinyl groups) and reduction in volatility when left at high temperature, the component (e) is a compound containing a vinyl group in the molecule, or a general formula ( A compound represented by VI), (VII) or (VIII) is preferred.

(Wherein R ⁵ and R ⁸ each independently represents an acryloyl group (CH ₂ ═CHCO—) or a methacryloyl group (CH ₂ ═C (CH ₃ ) CO—), and R ⁶ and R ⁷ each independently represent A hydrogen atom or a methyl group, t, u, v, w, x, and y each independently represent an integer of 1 to 8)

The compound containing a vinyl group in the molecule or the compound represented by the general formula (VI), (VII) or (VIII) is specifically an acid phosphooxyethyl methacrylate (bis ((2-methacryloyloxy)). Ethyl) phosphate), acid phosphooxyethyl acrylate (bis ((2-acryloyloxy) ethyl) phosphate), acid phosphooxypropyl methacrylate (bis ((2-methacryloyloxy) propyl) phosphate), acid phosphooxypolyoxyethylene glycol Monomethacrylate, acid phosphooxypolyoxypropylene glycol monomethacrylate, 2,2'-diacryloyloxydiethyl phosphate, 2,2'-dimethacryloyloxydiethyl phosphate, EO-modified phosphate dimethacrylate Phosphoric acid-modified epoxy acrylate, vinyl phosphoric acid, and compounds represented by the formula (XVII) can be mentioned.

  Of the components (e) shown above, compounds containing one or more acryloyl groups or methacryloyl groups in the molecule are particularly preferred.

  It is preferable that content of (e) component of this invention is 0.1-10 mass parts with respect to 100 mass parts of (a) component. By being 0.1-10 mass parts, the favorable adhesiveness to the board | substrate under high-humidity high temperature conditions can be expressed. It is more preferable that it is 0.2-5 mass parts, and it is further more preferable that it is 0.5-3 mass parts.

  In the composition of the present invention, for example, 90% by weight or more, 95% by weight or more, 98% by weight or more, and 100% by weight may comprise the components (a) to (e).

[Other ingredients]
In the photosensitive resin composition according to the present invention, in addition to the above components (a) to (e), if necessary, (1) a silane coupling agent, (2) a dissolution accelerator, (3) a dissolution inhibitor, (4) You may mix | blend components, such as surfactant or a leveling agent.

((1) Silane coupling agent)
Usually, the silane coupling agent is polymerized by itself in the step of heat-treating after coating, exposing and developing the photosensitive resin composition, in the step of reacting with the component (a) to crosslink or heat-treat. It is estimated that. Thereby, the adhesiveness of the cured film obtained and a board | substrate can be improved more. Particularly in the present invention, by using a silane coupling agent having a urea bond in the molecule in addition to the composition of the present invention, even when cured at a low temperature of 250 ° C. or lower, the adhesion to the substrate is further enhanced. be able to.

（式中、Ｒ^３１及びＲ^３２は、各々独立に炭素数１〜５のアルキル基である。ａは、１〜１０の整数であり、ｂは、１〜３の整数である。） Preferable silane coupling agents include compounds having a urea bond (—NH—CO—NH—), and the following formula (XVIII) is used because of excellent adhesion when cured at low temperature. The compounds represented are more preferred.

(In the formula, R ³¹ and R ³² are each independently an alkyl group having 1 to 5 carbon atoms. A is an integer of 1 to 10, and b is an integer of 1 to 3.)

  Specific examples of the compound represented by the formula (XVIII) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, and 3-ureidopropyltrimethoxysilane. , 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, and the like, preferably 3-ureidopropyltriethoxysilane.

Further, when a silane coupling agent having a hydroxy group or a glycidyl group in addition to the silane coupling agent having a urea bond in the molecule is used in combination, there is an effect of improving the adhesion of the cured film to the substrate during low temperature curing.
Examples of the silane coupling agent having a hydroxy group or a glycidyl group include methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert- Butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenyl Silanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, Sobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene, 1,4-bis (ethyldihydroxysilyl) benzene, 1,4-bis (propyldihydroxysilyl) benzene, , 4-bis (butyldihydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) Benzene, 1,4-bis (dipropyl hydroxy silyl) benzene, and 1,4-bis (dibutyl hydroxy silyl) benzene, and a compound represented by the following general formula (XVIV).

（式（XVIV）中、Ｒ^３３はヒドロキシ基又はグリシジル基を有する１価の有機基、Ｒ^３４及びＲ^３５は各々独立に炭素数１〜５のアルキル基である。ｃは１〜１０の整数、ｄは０〜２の整数である。）

(In formula (XVIV), R ³³ is a monovalent organic group having a hydroxy group or a glycidyl group, R ³⁴ and R ³⁵ are each independently an alkyl group having 1 to 5 carbon atoms. C is an integer of 1 to 10) , D is an integer of 0-2.)

Among the above compounds, a compound represented by the general formula (XVIV) is particularly preferable because it improves the adhesion to the substrate.
Such silane coupling agents include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyl. Triethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycid Xylethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybuty Triethoxysilane, and the like.

  The silane coupling agent having a hydroxy group or glycidyl group is preferably a silane coupling agent having a group containing a nitrogen atom, specifically an amino group or an amide bond, together with the hydroxy group or glycidyl group. Examples of the silane coupling agent having an amino group include bis (2-hydroxymethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane, and bis (2-glycidoxy). And methyl) -3-aminopropyltriethoxysilane and bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane.

Examples of the silane coupling agent having an amide bond include silane coupling agents having an amide bond such as a compound represented by the following formula.
_{X- (CH 2) e -CO-} NH- (CH 2) f -Si (OR) 3
(X is a hydroxy group or a glycidyl group, e and f are each independently an integer of 1 to 3, and R is a methyl group, an ethyl group or a propyl group.)

  When the silane coupling agent is used, the content is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the component (a). More preferably, it is 3-10 mass parts.

((2) dissolution promoter)
In the present invention, a dissolution accelerator may be added in order to further promote the solubility of the component (a) in the alkaline aqueous solution. Examples of the dissolution accelerator include compounds having a phenolic hydroxyl group. When the compound having a phenolic hydroxyl group is added to the photosensitive resin composition, the development speed of the exposed portion increases when developing with an alkaline aqueous solution, and the sensitivity is increased. During curing, the photosensitive resin film can be prevented from melting.

  The compound having a phenolic hydroxyl group is not particularly limited, but a compound having a relatively small molecular weight is preferable. Such compounds include o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, bisphenol A, B, C, E, F and G, 4,4 ′, 4 ″ -methylidynetrisphenol, 2,6-[(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol, 4,4 ′-[1- [4- [1 -(4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 4,4 '-[1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethylidene] bisphenol, 4,4 ′, 4 ″ -Ethyridine trisphenol, 4- [bis (4-hydroxyphenyl) methyl] -2-ethoxyphenol, 4,4 ′-[(2-hydro Cyphenyl) methylene] bis [2,3-dimethylphenol], 4,4 ′-[(3-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4 ′-[(4-hydroxyphenyl) Methylene] bis [2,6-dimethylphenol], 2,2 ′-[(2-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 2,2 ′-[(4-hydroxyphenyl) methylene] Bis [3,5-dimethylphenol], 4,4 ′-[(3,4-dihydroxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4- [bis (3-cyclohexyl-4-hydroxy) -6-methylphenyl) methyl] -1,2-benzenediol, 4,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] -1 2,3-benzenetriol, 4,4 ′-[(2-hydroxyphenyl) methylene] bis [3-methylphenol], 4,4 ′, 4 ″-(3-methyl-1-propanyl-3-ylidine ) Trisphenol, 4,4 ′, 4 ″, 4 ′ ″-(1,4-phenylenedimethylidine) tetrakisphenol, 2,4,6-tris [(3,5-dimethyl-4-hydroxyphenyl) Methyl] -1,3-benzenediol, 2,4,6-tris [(3,5-dimethyl-2-hydroxyphenyl) methyl] -1,3-benzenediol, 4,4 ′-[1- [4 -[1- (4-Hydroxyphenyl) -3,5-bis [(hydroxy-3-methylphenyl) methyl] phenyl] -phenyl] ethylidene] bis [2,6-bis (hydroxy-3-methylphenyl) ) Methyl] phenol and the like.

  In the case of using a dissolution accelerator, the content is preferably 1 to 30 parts by weight, and 3 to 25 parts by weight with respect to 100 parts by weight of component (a), from the viewpoint of the development time and the allowable width of the unexposed part remaining film ratio. Part is more preferred.

((3) dissolution inhibitor)
In the present invention, a dissolution inhibitor that is a compound that inhibits the solubility of the component (a) in an alkaline aqueous solution can be contained. The dissolution inhibitor is useful for adjusting the remaining film thickness and the development time by inhibiting the solubility of the component (a). On the other hand, since the generated acid is easily volatilized, it is considered that it does not participate in the cyclization dehydration reaction of polyamic acid (polyimide precursor) or polyhydroxyamide (polybenzoxazole precursor).

  Preferred compounds that can be used as dissolution inhibitors are diphenyliodonium salts such as diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, and diphenyliodonium iodide. As mentioned.

  In the case of using a dissolution inhibitor, the blending amount is preferably 0.01 to 50 parts by mass, and 0.01 to 30 parts by mass with respect to 100 parts by mass of the component (a), from the viewpoint of sensitivity and an allowable range of development time. More preferably, 0.1-20 mass parts is further more preferable.

((4) Surfactant or leveling agent)
In addition, a surfactant or a leveling agent may be added to the photosensitive resin composition of the present invention in order to improve applicability (for example, suppression of striation (film thickness unevenness)) and developability.

  Examples of such surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like. “Megafax F171”, “F173”, “R-08” (above, manufactured by Dainippon Ink & Chemicals, Inc.), trade names “Florard FC430”, “FC431” (above, manufactured by Sumitomo 3M Limited), trade names “Organosiloxane polymer KP341”, “KBM303”, “KBM403”, “KBM803” (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

  In the case of using a surfactant or a leveling agent, the content is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of component (a) from the viewpoint of compatibility with each component and volatility when left at high temperature. 0.1 to 3 parts by mass is more preferable.

[Method for producing patterned cured film]
Next, the manufacturing method of the pattern cured film by this invention is demonstrated. The method for producing a cured pattern film of the present invention comprises a step of forming a photosensitive resin film to form a photosensitive resin film by applying and drying the photosensitive resin composition of the present invention on a support substrate, the coating and drying step. A step of exposing the photosensitive resin film obtained by the above to a predetermined pattern, 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 contains. Hereinafter, each step will be described.

(Photosensitive resin film forming process)
First, in this step, the photosensitive resin composition of the present invention is spinner or the like on a substrate of glass, semiconductor, metal oxide insulator (for example, TiO ₂ , SiO _2, etc.), silicon nitride, copper, copper alloy or the like. Is then spin-coated using, and then dried using a hot plate, oven, or the like. The heating temperature at this time is preferably 80 to 150 ° C. Thereby, the photosensitive resin film which formed the photosensitive resin composition in the film form is obtained.

(Exposure process)
Next, in the exposure step, exposure is performed by irradiating the photosensitive resin film formed as a film on the support substrate with an actinic ray such as ultraviolet ray, visible ray, or radiation via a mask. As the exposure apparatus, for example, an exposure apparatus having a high-pressure mercury lamp or a low-pressure mercury lamp, an I-line stepper capable of irradiation with monochromatic light of 365 nm (i-line), an equilibrium exposure machine, a projection exposure machine, a scanner exposure machine, etc. can be used. .

(Development process)
The development step is a step of obtaining a patterned photosensitive resin film by treating the photosensitive resin film after the exposure step with a developer. In general, when a positive photosensitive resin composition is used, an exposed portion is removed with a developer, and when a negative photosensitive resin composition is used, an unexposed portion is removed with a developer. .
As the developer, for example, an aqueous alkali solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide is preferable, and tetramethylammonium is preferable. It is preferable to use a hydroxide. The concentration of these aqueous solutions is preferably 0.1 to 10% by mass. Further, an alcohol or a surfactant 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 mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the developer.

(Heat treatment process)
Next, in the heat treatment step, the patterned photosensitive resin film obtained in the development step is subjected to heat treatment, whereby when the component (a) is a polyamic acid, dehydration cyclization is performed to give an imide ring, (a) When the component is a polyhydroxyamide, it is dehydrated and closed to give an oxazole ring. At the same time, a crosslinked structure or the like can be formed between the functional groups of the component (a) or between the components (a) and (d) to form a pattern cured film.
The heating temperature in the heat treatment step is preferably 280 ° C. or lower, more preferably 120 to 280 ° C., further preferably 160 to 250 ° C., and particularly preferably 160 to 200 ° C.

Examples of the apparatus used for the heat treatment step include a quartz tube furnace, a hot plate, rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace. Moreover, although it can select either in air | atmosphere or inert atmosphere, such as nitrogen, since it is more preferable to perform under nitrogen, the oxidation of the photosensitive resin composition film | membrane 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.

Further, as the heat treatment of the present invention, a microwave curing device or a frequency variable 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 resin composition film while keeping the temperature of the substrate or device at, for example, 220 ° C. or lower (see, for example, Japanese Patent No. 2587148).
When curing is performed using microwaves, it is preferable to irradiate the microwaves in pulses while changing the frequency, because standing waves can be prevented and the substrate surface can be heated uniformly. Furthermore, when the substrate includes metal wiring like an electronic component, it is possible to prevent the occurrence of electric discharge from the metal and to protect the electronic component from destruction by irradiating the microwave in pulses while changing the frequency. This is preferable. Further, it is preferable to irradiate the microwaves in a pulsed manner in that the set heating temperature can be maintained and damage to the photosensitive resin film and the substrate can be avoided.

  The time for dehydrating and ring-closing the polybenzoxazole precursor in the photosensitive resin composition of the present invention is the time until the dehydrating and ring-closing reaction sufficiently proceeds, but is generally about 5 hours or less in view of work efficiency. The atmosphere of dehydration ring closure can be selected from the air or an inert atmosphere such as nitrogen.

[Semiconductor device manufacturing process]
Next, as an example of a method for producing a patterned cured film according to the present invention, a process for producing a semiconductor device will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view of a semiconductor device having a rewiring structure according to an embodiment of the present invention. The semiconductor device of this embodiment has a multilayer wiring structure. An Al wiring layer 2 is formed on the interlayer insulating layer (interlayer insulating film) 1, and an insulating layer (insulating film) 3 (for example, a P-SiN layer) is further formed on the Al wiring layer 2. A (surface protective film) 4 is formed. A rewiring layer 6 is formed from the pad portion 5 of the wiring layer 2 and extends to an upper portion of the core 8 which is a connection portion with a conductive ball 7 formed of solder, gold or the like as an external connection terminal. Further, a cover coat layer 9 is formed on the surface protective layer 4. The rewiring layer 6 is connected to the conductive ball 7 through the barrier metal 10, and a collar 11 is provided to hold the conductive ball 7. When a package having such a structure is mounted, an underfill 12 may be interposed in order to further relieve stress.

  In this figure, the photosensitive resin composition of the present invention is not only suitable as an interlayer insulating layer and a surface protective layer but also as a material for a cover coat layer, a core, a collar, an underfill, etc. because of its excellent characteristics. . Since the heat-resistant photosensitive resin cured body using the photosensitive resin composition of the present invention is excellent in adhesiveness with a metal layer, a sealant and the like and has a high stress relaxation effect, the photosensitive resin composition of the present invention A semiconductor element in which the obtained heat-resistant photosensitive resin cured product is used for a cover coat layer, a core, a collar, an underfill, etc. has extremely excellent reliability.

  The semiconductor device of the present invention has an interlayer insulating layer, a surface protective layer, a cover coat, a core for rewiring, a color for balls such as solder, or an underfill formed using the photosensitive resin composition of the present invention. Other than that, there is no particular limitation, and various structures can be adopted.

  In the present invention, in a heating process for forming a patterned cured film, which conventionally required a high temperature of around 350 ° C., curing can be performed using low-temperature heating at 250 ° C. or lower. Even in the case of curing at 250 ° C. or lower, the photosensitive resin composition of the present invention undergoes sufficient cyclization dehydration reaction, so that the film physical properties (elongation, water absorption, weight loss temperature, outgas, etc.) are cured at 300 ° C. or higher. The change in physical properties is small as compared with the case of the above. Therefore, since the process can be performed at a low temperature, defects due to the heat of the device can be reduced, and a highly reliable semiconductor device (electronic component) can be obtained with a high yield. Furthermore, even when cured at 200 ° C. or lower, it has sufficient film properties.

[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 cured film formed by the above-described manufacturing method using the above-described photosensitive resin composition. Here, the electronic component includes a semiconductor device, a multilayer wiring board, various electronic devices, and the like.

  Moreover, the said pattern cured film can be specifically used for formation of the surface insulation film of an electronic component, such as a semiconductor device, the interlayer insulation film, etc., the interlayer insulation film of a multilayer wiring board, etc. The electronic component according to the present invention is not particularly limited except that it has a surface protective film, an interlayer insulating film, and the like formed using the photosensitive resin composition, and can have various structures.

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

[Synthesis of polyhydroxyamide (polybenzoxazole precursor)]
Synthesis example 1
A 0.2 liter flask equipped with a stirrer and a thermometer was charged with 60 g of N-methylpyrrolidone, and 13.92 g (38 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added. And dissolved with stirring. Subsequently, 9.56 g (40 mmol) of sebacic acid dichloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5 ° C., and then stirring was continued for 60 minutes.
The solution was poured into 3 liters of water, the precipitate was collected, washed with pure water three times, and then decompressed to obtain polyhydroxyamide (hereinafter referred to as polymer I). The weight average molecular weight calculated | required by GPC method standard polystyrene conversion of the polymer I was 33,100, and dispersion degree was 2.0.

In addition, the measurement conditions of the weight average molecular weight by GPC method are as follows.
Measuring device: Detector L4000 UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
C-R4A Chromatopac manufactured by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 x2 eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / l), H ₃ PO ₄ (0.06 mol / l)
Flow rate: 1.0 ml / min, detector: UV 270 nm
The measurement was performed using a solution of 1 ml of a solvent [THF / DMF = 1/1 (volume ratio)] with respect to 0.5 mg of the polymer.

Synthesis example 2
The synthesis was performed under the same conditions as in Synthesis Example 1 except that sebacic acid dichloride used in Synthesis Example 1 was replaced with dodecanedioic acid dichloride. The obtained polyhydroxyamide (hereinafter referred to as polymer II) had a weight average molecular weight of 31,600 and a dispersity of 2.0 determined by standard polystyrene conversion.

Synthesis example 3
The synthesis was performed under the same conditions as in Synthesis Example 1 except that sebacic acid dichloride used in Synthesis Example 1 was replaced with adipic acid dichloride. The obtained polyhydroxyamide (hereinafter referred to as polymer III) had a weight average molecular weight of 29,300 and a dispersity of 1.9, as determined by standard polystyrene conversion.

Synthesis example 4
A 0.2 liter flask equipped with a stirrer and a thermometer was charged with 60 g of N-methylpyrrolidone, and 13.92 g (38 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added. And dissolved with stirring. Subsequently, while maintaining the temperature at 0 to 5 ° C., 7.65 g (32 mmol) of sebacic acid dichloride and 2.36 g (8 mmol) of 4,4′-diphenyl ether dicarboxylic acid dichloride were added dropwise each for 10 minutes, and then returned to room temperature. Stirring was continued for 3 hours.
The solution was poured into 3 liters of water, and the precipitate was collected, washed with pure water three times, and then decompressed to obtain polyhydroxyamide (hereinafter referred to as polymer IV). The weight average molecular weight of polymer IV determined by GPC standard polystyrene conversion was 32,500, and the degree of dispersion was 2.2.

Synthesis example 5
A 0.2 liter flask equipped with a stirrer and a thermometer was charged with 60 g of N-methylpyrrolidone, and 13.92 g (38 mmol) of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added. Added and stirred to dissolve. Subsequently, while maintaining the temperature at 0 to 5 ° C., 8.55 g (32 mmol) of dodecanedioic acid dichloride and 2.36 g (8 mmol) of 4,4′-diphenyl ether dicarboxylic acid dichloride were added dropwise each for 10 minutes, and then the mixture was brought to room temperature. The stirring was continued for 3 hours.
The solution was poured into 3 liters of water, the precipitate was collected, washed with pure water three times, and then decompressed to obtain polyhydroxyamide (hereinafter referred to as polymer V). The polymer V had a weight average molecular weight of 39,500 and a dispersity of 1.9 determined by GPC standard polystyrene conversion.

Synthesis Example 6
The synthesis was carried out under the same conditions as in Synthesis Example 1 except that sebacic acid dichloride used in Synthesis Example 1 was replaced with 4,4′-diphenyl ether dicarboxylic acid dichloride. The obtained polyhydroxyamide (hereinafter referred to as polymer VI) had a weight average molecular weight of 16,900 and a dispersity of 1.7 determined by standard polystyrene conversion.

[Synthesis of polyimide]
Synthesis example 7
1.75 g of 3,5-diaminobenzoic acid (molecular weight 152.2), aliphatic ether diamine ("D-400", polyoxyalkylene diamine) in a flask equipped with a stirrer, thermometer, condenser, and nitrogen displacement device Manufactured by BASF (trade name), molecular weight 452.4) 15.38 g and 1,1,3,3-tetramethyl-1,3-bis (4-aminophenyl) disiloxane ("LP-7100", Shin-Etsu) Chemicals, trade name) Molecular weight 248.5) 0.37 g and N-methylpyrrolidone 105 g were charged. Next, 16.32 g of 4,4′-oxydiphthalic dianhydride (molecular weight 326.3) was added to the flask in small portions while the flask was cooled in an ice bath. After completion of the addition, the mixture was further stirred at room temperature for 5 hours.
Next, a reflux condenser with a moisture receiver was attached to the flask, 70 g of xylene was added, the temperature was raised to 180 ° C. while blowing nitrogen gas, the temperature was maintained for 5 hours, and xylene was removed azeotropically with water. . The solution thus obtained was cooled to room temperature and then poured into distilled water for reprecipitation.
The resulting precipitate was dried with a vacuum dryer to obtain polyimide (hereinafter referred to as polymer VII). When GPC of the obtained polyimide resin was measured, it was Mw = 33000 and dispersity was 2.2 in terms of polystyrene.

Examples 1-17, Comparative Examples 1-3
Components (b) to (e) were blended in the blending amounts shown in Table 1 with respect to 100 parts by mass of each polymer as the component (a) to obtain a solution of a photosensitive resin composition. The unit of numerical values in Table 1 is parts by mass.
B1, B2, D1 to D5, and E1 to E5 are shown below.
B1 and B2 are components (b).
D1 to D5 are components (d).
E1 to E4 are components (e), but E5 is not a component (e).
As the component (c), BLO (γ-butyrolactone), EL (ethyl lactate), or NMP (N-methylpyrrolidone) was used.

Ｄ１：４，４’−（１−フェニルエチリデン）ビス［２，６−ビス（ヒドロキシメチル）フェノール］
Ｄ２：１，３，４，６−テトラキス（メトキシメチル）グリコウリル
Ｄ３：４，４’−メチレンビス（２−メチル−６−ヒドロキシメチルフェノール）
Ｄ４：２，２−ビス（４−グリシジルオキシフェニル）プロパン
Ｄ５：ビス（３−エチルオキセタン−３−イルメチル）エーテル
Ｅ１：リン酸ジブチル（東京化成工業（株）製）
Ｅ２：ビニルホスホン酸（東京化成工業（株）製）
Ｅ３：カヤマーＰＭ−２（ビス（（２−メタクリロイルオキシ）エチル）ホスフェート、日本化薬（株）製、商品名）
Ｅ４：カヤマーＰＭ−２１（カプロラクトン変性リン酸時メタクリレート、日本化薬（株）製、商品名）
Ｅ５：トリデシルホスフィンオキシド（東京化成工業（株）製）

D1: 4,4 ′-(1-Phenylethylidene) bis [2,6-bis (hydroxymethyl) phenol]
D2: 1,3,4,6-tetrakis (methoxymethyl) glycoluril D3: 4,4'-methylenebis (2-methyl-6-hydroxymethylphenol)
D4: 2,2-bis (4-glycidyloxyphenyl) propane D5: bis (3-ethyloxetane-3-ylmethyl) ether E1: dibutyl phosphate (manufactured by Tokyo Chemical Industry Co., Ltd.)
E2: Vinylphosphonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
E3: Kayamar PM-2 (Bis ((2-methacryloyloxy) ethyl) phosphate, manufactured by Nippon Kayaku Co., Ltd., trade name)
E4: Kayamar PM-21 (Caprolactone-modified phosphoric acid methacrylate, Nippon Kayaku Co., Ltd., trade name)
E5: Tridecylphosphine oxide (manufactured by Tokyo Chemical Industry Co., Ltd.)

Evaluation 1
About the photosensitive resin composition prepared in Examples 1-17 and Comparative Examples 1-3, the sensitivity and the dissolution rate at the time of forming a pattern cured film were evaluated. Specifically, the photosensitive resin compositions prepared in Examples 1 to 17 and Comparative Examples 1 to 3 were spin coated on a silicon substrate and a copper substrate, respectively, to form a resin film having a dry film thickness of 10 to 12 μm. did. The obtained resin film was exposed by irradiating a predetermined pattern with i-rays of 100 to 1000 mJ / cm ² through an interference filter using an ultrahigh pressure mercury lamp. After the exposure, development was performed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) until the exposed silicon substrate or copper substrate was exposed, followed by rinsing with water to obtain a patterned resin film.
The following evaluation was implemented about the obtained pattern resin film.

(1) Sensitivity evaluation In pattern resin film formation on a silicon substrate, it is necessary for the pattern of the exposed area to open when the remaining film ratio of the unexposed area (ratio of film thickness before and after development) is 80%. The minimum exposure (sensitivity) was determined. The exposure was performed by pattern irradiation while increasing the exposure amount in increments of 100 mJ / cm ² to 10 mJ / cm ² , and the minimum exposure amount was judged while observing the opening pattern with a microscope. The results are shown in Table 2.

(2) Sensitivity difference between substrates Similarly, when forming a patterned resin film on a copper substrate, the pattern of the exposed area is opened when the remaining film ratio of the unexposed area (ratio of film thickness before and after development) is 80%. The minimum exposure amount (sensitivity) required for the determination was obtained. The results are shown in Table 2. Based on the sensitivity in forming the pattern resin film on the silicon substrate, the difference between the sensitivity in forming the pattern resin film on the silicon substrate and the sensitivity in the pattern resin film on the copper substrate was less than 10%. This is indicated by B.

(3) Difference in dissolution rate between substrates In forming a patterned resin film on a silicon substrate and a copper substrate, the dissolution rate of the unexposed area was determined based on the time required for development. The dissolution rate was determined by dividing the film thickness dissolved within a predetermined time (curtain thickness before development−film thickness after development) by time ((dissolved film thickness) ÷ (dissolution time)). The results are shown in Table 2. The difference between the dissolution rate in forming the pattern resin film on the silicon substrate and the dissolution rate in the pattern resin film on the copper substrate was less than 10% based on the dissolution rate in forming the pattern resin film on the silicon substrate. A and 10% or more are indicated by B.

Evaluation 2
A cured pattern film was produced from the patterned resin film prepared in Evaluation 1, and the adhesion and chemical resistance were evaluated. Specifically, after heating the silicon substrate with a pattern resin film and the copper substrate with a pattern resin film using a vertical diffusion furnace μ-TF (manufactured by Koyo Thermo Systems Co., Ltd.) at 100 ° C. for 1 hour, It heated at 250 degreeC or 200 degreeC for 1 hour, and obtained the pattern cured film (5-10 micrometers in film thickness after hardening).
The following evaluation was implemented about the obtained pattern resin film.

(1) Evaluation of adhesiveness The adhesiveness with respect to the board | substrate of a pattern cured film was evaluated using the stud pull method using the manufactured copper substrate with a pattern cured film (curing temperature 250 degreeC and / or 200 degreeC). The results are shown in Table 2. Specifically, the stud pull method is an aluminum pin with an epoxy resin on a patterned cured film of a copper substrate with a patterned cured film treated for 100 hours under high temperature and high humidity conditions (131 ° C./85 RH%). Then, the stud pin with the epoxy resin was adhered to the cured film by heating in an oven at 150 ° C. for 1 hour. This pin was pulled using ROMULUS (manufactured by Quad Group Inc.), and the peeled state when peeled off was visually observed.
Adhesive strength of 600 kg / cm ² or more is A, adhesive strength is less than 600 kg / cm ² , but when peeled from the interface between the cured film and the epoxy resin, or the interface between the epoxy resin and the aluminum pin, B, copper The case where it peeled in the interface of a board | substrate and a cured film was evaluated as C, respectively. The results are shown in Table 2.
The adhesion evaluation as described above was similarly performed on a cured film in which the treatment time under high temperature and high humidity conditions was 200 hours and 300 hours. The results are shown in Table 2.

(2) Evaluation of chemical resistance Next, using a pattern cured film (curing temperature 250 ° C. and / or 200 ° C.) (film thickness after curing 5 to 10 μm) prepared on a silicon substrate in the same manner as above, With respect to the cured film, changes in the cured film were observed when each of acetone, BLO, and NMP was immersed for 15 minutes at room temperature. Crack or peeling does not occur, change in film thickness before and after immersion is 1 μm or less A, crack or peeling does not occur, change in film thickness before and after immersion is greater than 1 μm, B crack occurs Although it was not, the thing which the cured film peeled from the board | substrate by swelling was set to C, and the thing into which the cured film cracked was set to D. The results are shown in Table 2.

In each of Examples 1 to 17, it was confirmed that the substrate adhesion under good high temperature and high humidity conditions and good chemical resistance were confirmed. In Examples 1 to 12 and 15 to 17, good substrate adhesion and chemical resistance were exhibited even when cured at a low temperature of 200 ° C. or lower.
On the other hand, in Comparative Example 1 in which no crosslinking agent was used, the chemical resistance was lowered. In Comparative Example 2 in which the component (e) was not used and in Comparative Example 3 in which the component (e) having no phosphoric acid group and phosphonic acid group was used, the results were poor in substrate adhesion and chemical resistance. In Comparative Examples 2 and 3, the substrate adhesion decreased particularly when curing was performed at a low temperature of 200 ° C.

  The photosensitive resin composition according to the present invention comprises (a) an alkali-soluble resin, (b) a photosensitive agent, (c) a solvent, (d) a crosslinking agent, and (e) a phosphate group or phosphonic acid in the molecule. By containing a group or a compound having a phosphinic acid group, performance comparable to that obtained by curing physical properties of the cured pattern film at a high temperature can be obtained. Moreover, according to the method for producing a pattern of the present invention, by using the photosensitive resin composition, sensitivity, excellent adhesion to a substrate under high temperature and high humidity conditions, and excellent heat resistance even in a low temperature curing process, A patterned cured film having a low water absorption and a good shape can be obtained. The pattern cured film obtained from the photosensitive resin composition of the present invention has excellent shape, adhesion, heat resistance, and can be cured by a low temperature process, thereby avoiding damage to the device and having high reliability. Parts are obtained.

DESCRIPTION OF SYMBOLS 1 Interlayer insulating layer 2 Al wiring layer 3 Insulating layer 4 Surface protective layer 5 Pad part 6 of wiring layer Rewiring layer 7 Conductive ball 8 Core 9 Cover coat layer 10 Barrier metal 11 Color 12 Underfill

Claims (9)

(A) an alkali-soluble resin having a structural unit represented by the general formula (I) ;
(B) a photosensitive agent;
(C) a solvent;
(D) a crosslinking agent;
(E) The photosensitive resin composition containing the compound represented by either of following formula (VI)-(VIII) .

(In the formula, U represents a divalent organic group, a single bond, —O—, or —SO ₂ —, V represents a divalent organic group, and at least V is an aliphatic group having 1 to 30 carbon atoms. Or a group including an aliphatic structure having 2 to 30 carbon atoms constituting the main chain.)

(Wherein R ⁵ and R ⁸ each independently represents an acryloyl group (CH ₂ ═CHCO—) or a methacryloyl group (CH ₂ ═C (CH ₃ ) CO—), and R ⁶ and R ⁷ each independently represent A hydrogen atom or a methyl group, t, u, v, w, x, and y each independently represent an integer of 1 to 8) The photosensitive resin composition according to claim 1 , wherein the component (d) is a compound having a methylol group or an alkoxyalkyl group. The photosensitive resin composition according to claim 1, wherein the component (b) is a compound that generates an acid or a radical by light. The photosensitive resin film obtained by the process of apply | coating and drying the photosensitive resin composition of any one of Claims 1-3 on a support substrate, and forming the photosensitive resin film, and the said application | coating and drying process. A process for exposing the exposed photosensitive resin film to a predetermined pattern, a process for developing the exposed photosensitive resin film using an alkaline aqueous solution, and a process for heat-treating the developed photosensitive resin film. . The method for producing a cured pattern film according to claim 4 , wherein the heat treatment temperature is 250 ° C. or lower in the step of heat-treating the photosensitive resin film after development. The method for producing a patterned cured film according to claim 4 , wherein the heat treatment temperature is 200 ° C. or lower in the step of heat-treating the photosensitive resin film after development. The interlayer insulation film using the pattern cured film obtained by the manufacturing method of the pattern cured film of any one of Claims 4-6 . The surface protective film using the pattern cured film obtained by the manufacturing method of the pattern cured film of any one of Claims 4-6 . An electronic component having the interlayer insulating film or surface protective film according to claim 7 or 8 .

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