JP2020144222A - Positive photosensitive resin composition, dry film, cured product, and electronic component - Google Patents

Abstract

To provide a positive photosensitive resin composition excellent in storage property and suitable for forming a multilayer structure, which allows formation of a pattern having a high taper angle and prevents generation of cracks by a solvent or deformation when thermally cured, a dry film having a resin layer obtained from the above composition, a cured product of the composition or of the resin layer of the dry film, and an electronic component having the cured product.SOLUTION: The positive photosensitive resin composition comprises (A) an alkali-soluble resin containing at least either a benzoxazole precursor structure or an imide precursor structure as a repeating unit, (B) a photosensitive agent, and (C) a filler having an average particle diameter of 2 μm or less.SELECTED DRAWING: None

Description

The present invention relates to positive photosensitive resin compositions, dry films, cured products, and electronic components.

In recent years, electronic components have become smaller and passive components have also become smaller. Among them, the parts forming the coil (inductor and choke coil) have been miniaturized from 2016 size (2 mm x 1.6 mm) to 0402 size (0.4 mm x 0.2 mm), and miniaturization is required. There is. One of the measures for miniaturization of such electronic components is miniaturization of circuit formation and laminated structure, and in recent years, a construction method using an organic insulating layer has been proposed instead of the laminated ceramic technology. For example, Patent Document 1 describes an inductor manufactured by laminating an insulating layer made of an organic substance and a layer made of a copper-plated electrode, and for forming an insulating layer for miniaturization (for example, pattern formation of 15 μm or less). It has been studied to use a photosensitive resin composition capable of forming a pattern by exposure and development.

On the other hand, the insulating layer in electronic components is required to have low dielectric properties from the viewpoint of transmission loss, and among them, a material made of polybenzoxazole or polyimide has been preferred. Therefore, in electronic components such as semiconductor chips, positive photosensitive resin compositions in which a precursor of polybenzoxazole or polyimide and a photosensitizer such as naphthoquinone diazide are combined are widely adopted.

Japanese Unexamined Patent Publication No. 2016-225611

However, in a positive photosensitive resin composition in which a precursor of polybenzoxazole or polyimide and a photosensitive agent such as naphthoquinonediazide are combined, the angle of the opening wall surface (so-called taper angle) becomes low in the pattern formation of the insulating layer, and the insulation is insulated. When the layers are laminated, the shape of the circuit (via) connecting the layers becomes fan-shaped, so it is difficult to obtain position accuracy, and there is a problem that the flatness deteriorates as the lamination is repeated in order to form multiple layers. .. Further, when forming a coil having a high multilayer structure using an organic insulating layer and plating due to the demand for miniaturization, the pattern opening of the organic insulating layer should form a high taper angle such as 70 to 90 °. Is required.

Further, in the positive photosensitive resin composition in which a precursor of conventional polybenzoxazole or polyimide and a photosensitive agent such as naphthoquinone diazide are combined, the taper angle is further reduced to 60 ° or less in thermosetting after pattern formation by development. Sometimes I did.

Further, when forming a laminated structure composed of an organic insulating layer, a resin composition for forming an upper insulating layer is applied over the upper layer of the lower insulating layer. In such a case, the lower insulating layer is exposed to the solvent contained in the resin composition for forming the upper insulating layer, and there is a problem that cracks are generated in the lower insulating layer. It was.

Further, such a photosensitive resin composition is also required to have long-term storage stability from the viewpoint of productivity.

Therefore, an object of the present invention is positive photosensitivity suitable for forming a laminated structure, which has excellent storage stability, can form a pattern with a high taper angle, and does not generate cracks due to a solvent or deform during thermosetting. An object of the present invention is to provide a resin composition, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and an electronic component having the cured product.

As a result of diligent studies in view of the above, the present inventors have found that in a positive photosensitive resin composition in which a precursor of polybenzoxazole or polyimide and a photosensitive agent such as naphthoquinone diazide are combined, the taper angle of the pattern opening is a developer. It is presumed that the taper angle will be low due to erosion due to erosion and thermal deformation due to melting during thermosetting, and by blending a filler with an average particle diameter of 2 μm or less in the positive photosensitive resin composition, a pattern with a high taper angle can be formed. We have found that it is possible, and further improve storage stability and crack resistance to a solvent, and have completed the present invention.

That is, the positive photosensitive resin composition of the present invention contains (A) an alkali-soluble resin containing at least one of a benzoxazole precursor structure and an imide precursor structure as a repeating unit, (B) a photosensitizer, and ( C) It is characterized by containing a filler having an average particle size of 2 μm or less.

In the positive photosensitive resin composition of the present invention, it is preferable that the alkali-soluble resin (A) contains a benzoxazole skeleton.

（一般式（１）中、Ｕはアミン成分の残基である２価の有機基であり、Ｒ’はカルボン酸成分の残基である２価の有機基であり、ＵおよびＲ’の少なくとも何れか一方は下記一般式（１−１）、（１−２）および（１−３）のいずれかのベンゾオキサゾール骨格を有する２価の有機基である。

（一般式（１−１）中、Ｒ_１〜Ｒ_４は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、または、一般式（１）中の窒素原子もしくはカルボニル基との直接結合のいずれかであり、同一であっても異なっていてもよい。Ｒ_５〜Ｒ_９は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、または、一般式（１）中の窒素原子もしくはカルボニル基との直接結合のいずれかであり、同一であっても異なっていてもよい。ただし、Ｒ_１〜Ｒ_４のうちいずれか一つ、および、Ｒ_５〜Ｒ_９のうちいずれか一つは共に、一般式（１）中の窒素原子との直接結合であるか、一般式（１）中のカルボニル基との直接結合である。）

（一般式（１−２）中、Ｒ_１０〜Ｒ_１４は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、または、一般式（１）中の窒素原子もしくはカルボニル基との直接結合のいずれかであり、同一であっても異なっていてもよい。Ｒ_１５〜Ｒ_１９は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、または、一般式（１）中の窒素原子もしくはカルボニル基との直接結合のいずれかであり、同一であっても異なっていてもよい。ただし、Ｒ_１０〜Ｒ_１４のうちいずれか一つ、および、Ｒ_１５〜Ｒ_１９のうちいずれか一つは共に、一般式（１）中の窒素原子との直接結合であるか、一般式（１）中のカルボニル基との直接結合である。Ｒ_２０、Ｒ_２１はそれぞれ水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基のいずれかであり、同一であっても異なっていてもよい。）

（一般式（１−３）中、Ｒ_２２〜Ｒ_２６は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、または、一般式（１）中の窒素原子もしくはカルボニル基との直接結合のいずれかであり、同一であっても異なっていてもよい。Ｒ_２７〜Ｒ_３１は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、または、一般式（１）中の窒素原子もしくはカルボニル基との直接結合のいずれかであり、同一であっても異なっていてもよい。ただし、Ｒ_２２〜Ｒ_２６のうちいずれか一つ、および、Ｒ_２７〜Ｒ_３１のうちいずれか一つは共に、一般式（１）中の窒素原子との直接結合であるか、一般式（１）中のカルボニル基との直接結合である。Ｒ_３２、Ｒ_３３はそれぞれ水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基のいずれかであり、同一であっても異なっていてもよい。） The positive photosensitive resin composition of the present invention is a polyamide resin in which the alkali-soluble resin (A) is a reaction product of an amine component and a carboxylic acid component, and is a repeating unit represented by the following general formula (1). It is preferable to have.

(In the general formula (1), U is a divalent organic group which is a residue of an amine component, R'is a divalent organic group which is a residue of a carboxylic acid component, and at least U and R'. One of them is a divalent organic group having a benzoxazole skeleton according to any one of the following general formulas (1-1), (1-2) and (1-3).

(In the general formula _(1-1), R 1 to R ₄ is a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group or a nitrogen atom or the carbonyl of the general formula (1) It is either a direct bond with a group and may be the same or different. R _{5 to} R ₉ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, or , It is either a direct bond with a nitrogen atom or a carbonyl group in the general formula (1), and may be the same or different. However, any one of R _{1 to} R ₄ and Any one of R _{5 to} R ₉ is either a direct bond with the nitrogen atom in the general formula (1) or a direct bond with the carbonyl group in the general formula (1).)

(In the general formula (1-2), R _{10 to} R ₁₄ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a nitrogen atom or a carbonyl in the general formula (1). It is either a direct bond with a group and may be the same or different. R _{15 to} R ₁₉ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, or , It is either a direct bond with a nitrogen atom or a carbonyl group in the general formula (1), and may be the same or different. However, any one of R _{10 to} R ₁₄ and Any one of R _{15 to} R ₁₉ is either a direct bond with the nitrogen atom in the general formula (1) or a direct bond with the carbonyl group in the general formula (1). R ₂₀ , R ₂₁ is any one of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, and an amino group, and may be the same or different.)

(In the general formula (1-3), R _{22 to} R ₂₆ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a nitrogen atom or a carbonyl in the general formula (1). It is either a direct bond with a group and may be the same or different. R _27- R ₃₁ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, or , It is either a direct bond with a nitrogen atom or a carbonyl group in the general formula (1), and may be the same or different. However, any one of R _{22 to} R ₂₆ , and Any one of R _{27 to} R ₃₁ is either a direct bond with the nitrogen atom in the general formula (1) or a direct bond with the carbonyl group in the general formula (1). R ₃₂ , R ₃₃ is any one of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, and an amino group, and may be the same or different.)

The positive photosensitive resin composition of the present invention is a surface treatment agent having a filler having an average particle diameter of 2 μm or less (C) having at least one of a phenyl group, an epoxy group, an aminophenyl group and a vinyl group. It is preferably treated spherical silica.

The dry film of the present invention is characterized by having a resin layer obtained by applying the positive photosensitive resin composition to the film and drying it.

The cured product of the present invention is characterized by being obtained by curing the resin layer of the positive photosensitive resin composition or the dry film.

The electronic component of the present invention is characterized by having the cured product.

According to the present invention, a positive photosensitive resin composition suitable for forming a laminated structure, which has excellent storage stability, can form a pattern with a high taper angle, and does not generate cracks due to a solvent or deform during thermosetting. A product, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and an electronic component having the cured product can be provided.

The positive photosensitive resin composition of the present invention is an alkali-soluble resin containing at least one of (A) a benzoxazole precursor structure and an imide precursor structure as a repeating unit (hereinafter, simply "(A) alkali-soluble resin"). It is also characterized by containing (also referred to as), (B) a photosensitizer, and (C) a filler having an average particle diameter of 2 μm or less (hereinafter, also simply referred to as “(C) filler”). Although the detailed mechanism is not clear, (C) by blending a filler with an average particle size of 2 μm or less, it is possible to form a pattern with a surprisingly high taper angle, and further, it has excellent storage stability and a cured product. The crack resistance to the solvent is also improved, and it becomes possible to obtain a positive photosensitive resin composition suitable for forming a laminated structure.

Further, it is preferable that the alkali-soluble resin (A) contains a benzoxazole skeleton. (C) When a filler having an average particle size of 2 μm or less is blended, the dielectric properties of the cured product and the strength of the cured product tend to decrease, probably because the cyclization efficiency of the benzoxazole precursor structure or the imide precursor structure decreases. However, by introducing a benzoxazole skeleton having a pre-cyclized structure into the (A) alkali-soluble resin, deterioration of dielectric properties and strength can be suppressed.

Hereinafter, the components contained in the positive photosensitive resin composition of the present invention will be described in detail.

[(A) Alkali-soluble resin containing at least one of a benzoxazole precursor structure and an imide precursor structure as a repeating unit]
In the alkali-soluble resin (A), the benzoxazole precursor structure (so-called hydroxyamide structure) and the imide precursor structure (so-called amic acid structure) are not particularly limited and are included in known and commonly used positive photosensitive resin compositions. The precursor structure that the polybenzoxazole precursor or the polyimide precursor has as a repeating structure may be used.

The alkali-soluble resin (A) is preferably a polyamide resin which is a reaction product of an amine component and a carboxylic acid component. Further, the alkali-soluble resin (A) preferably contains a benzoxazole skeleton as described above. The benzoxazole skeleton is not particularly limited, and a benzobisoxazole skeleton may be used. Further, as the benzoxazole skeleton, a benzoxazole skeleton to which a benzene ring is bonded as shown by the general formulas (1-1) to (1-3) described later can also be preferably used.

The polymer terminal structure of the polyamide resin is not particularly limited, and examples thereof include amine component residues, carboxylic acid component residues, unsaturated double bonds, hydroxyl groups, and thiol groups.

The alkali-soluble resin (A) preferably contains a benzoxazole skeleton in the main chain skeleton. The method for introducing the benzoxazole skeleton is not particularly limited. For example, in the case of a polyamide resin, the polyamide resin may be synthesized using a compound having a benzoxazole skeleton as either an amine component or a carboxylic acid component. The ratio of the number of benzoxazole skeletons to the number of amide bonds of the polyamide resin is preferably 0.1 to 20%, more preferably 0.1 to 10%. When the benzoxazole skeleton in the polyamide resin is 0.1% or more, the heat resistance, dielectric properties, and film strength of the resin are improved, and when it is 20% or less, the alkali solubility is not impaired.

The alkali-soluble resin (A) is more preferably a polyamide resin having a repeating unit containing a benzoxazole skeleton represented by the following general formula (1) in the polyamide structure.

（一般式（１）中、Ｕはアミン成分の残基である２価の有機基であり、Ｒ’はカルボン酸成分の残基である２価の有機基であり、ＵおよびＲ’の少なくとも何れか一方は下記一般式（１−１）、（１−２）および（１−３）のいずれかのベンゾオキサゾール骨格を有する２価の有機基である。アミン成分およびカルボン酸成分の例としては、後述する（ａ）ジアミン成分、（ｂ）ジヒドロキシジアミン成分、（ｃ）トリまたはテトラカルボン酸無水物成分、および、（ｄ）ジカルボン酸成分で挙げた化合物と同様のものが挙げられる。）

（一般式（１−１）中、Ｒ_１〜Ｒ_４は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、または、一般式（１）中の窒素原子もしくはカルボニル基との直接結合のいずれかであり、同一であっても異なっていてもよい。Ｒ_５〜Ｒ_９は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、または、一般式（１）中の窒素原子もしくはカルボニル基との直接結合のいずれかであり、同一であっても異なっていてもよい。ただし、Ｒ_１〜Ｒ_４のうちいずれか一つ、および、Ｒ_５〜Ｒ_９のうちいずれか一つは共に、一般式（１）中の窒素原子との直接結合であるか、一般式（１）中のカルボニル基との直接結合である。）

（一般式（１−２）中、Ｒ_１０〜Ｒ_１４は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、または、一般式（１）中の窒素原子もしくはカルボニル基との直接結合のいずれかであり、同一であっても異なっていてもよい。Ｒ_１５〜Ｒ_１９は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、または、一般式（１）中の窒素原子もしくはカルボニル基との直接結合のいずれかであり、同一であっても異なっていてもよい。ただし、Ｒ_１０〜Ｒ_１４のうちいずれか一つ、および、Ｒ_１５〜Ｒ_１９のうちいずれか一つは共に、一般式（１）中の窒素原子との直接結合であるか、一般式（１）中のカルボニル基との直接結合である。Ｒ_２０、Ｒ_２１はそれぞれ水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基のいずれかであり、同一であっても異なっていてもよい。）

（一般式（１−３）中、Ｒ_２２〜Ｒ_２６は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、または、一般式（１）中の窒素原子もしくはカルボニル基との直接結合のいずれかであり、同一であっても異なっていてもよい。Ｒ_２７〜Ｒ_３１は水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基、または、一般式（１）中の窒素原子もしくはカルボニル基との直接結合のいずれかであり、同一であっても異なっていてもよい。ただし、Ｒ_２２〜Ｒ_２６のうちいずれか一つ、および、Ｒ_２７〜Ｒ_３１のうちいずれか一つは共に、一般式（１）中の窒素原子との直接結合であるか、一般式（１）中のカルボニル基との直接結合である。Ｒ_３２、Ｒ_３３はそれぞれ水素原子、有機基、ニトロ基、ハロゲン原子、スルホ基、スルホニル基、アミノ基のいずれかであり、同一であっても異なっていてもよい。）

(In the general formula (1), U is a divalent organic group which is a residue of an amine component, R'is a divalent organic group which is a residue of a carboxylic acid component, and at least U and R'. One of them is a divalent organic group having a benzoxazole skeleton according to any one of the following general formulas (1-1), (1-2) and (1-3). As an example of an amine component and a carboxylic acid component. (A) Diamine component, (b) Dihydroxydiamine component, (c) Tri or tetracarboxylic acid anhydride component, and (d) Dicarboxylic acid component, which will be described later.

(In the general formula (1-1), R _{1 to} R ₄ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a nitrogen atom or a carbonyl in the general formula (1). It is either a direct bond with a group and may be the same or different. R _{5 to} R ₉ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, or , It is either a direct bond with a nitrogen atom or a carbonyl group in the general formula (1), and may be the same or different. However, any one of R _{1 to} R ₄ and Any one of R _{5 to} R ₉ is either a direct bond with a nitrogen atom in the general formula (1) or a direct bond with a carbonyl group in the general formula (1).)

(In the general formula (1-2), R _{10 to} R ₁₄ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a nitrogen atom or a carbonyl in the general formula (1). It is either a direct bond with a group and may be the same or different. R _{15 to} R ₁₉ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, or , It is either a direct bond with a nitrogen atom or a carbonyl group in the general formula (1), and may be the same or different. However, any one of R _{10 to} R ₁₄ and Any one of R _{15 to} R ₁₉ is either a direct bond with the nitrogen atom in the general formula (1) or a direct bond with the carbonyl group in the general formula (1). R ₂₀ , R ₂₁ is any one of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, and an amino group, and may be the same or different.)

(In the general formula (1-3), R _{22 to} R ₂₆ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a nitrogen atom or a carbonyl in the general formula (1). It is either a direct bond with a group and may be the same or different. R _27- R ₃₁ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, or , It is either a direct bond with a nitrogen atom or a carbonyl group in the general formula (1), and may be the same or different. However, any one of R _{22 to} R ₂₆ , and Any one of R _{27 to} R ₃₁ is either a direct bond with the nitrogen atom in the general formula (1) or a direct bond with the carbonyl group in the general formula (1). R ₃₂ , R ₃₃ is any one of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, and an amino group, and may be the same or different.)

R _{1 to} R ₄ and R _{5 to} R _{9 in} the general formula (1-1), R _{10 to} R ₁₄ and R _{15 to} R ₁₉ in the general formula (1-2), and the general formula (1-). It is preferable that R _{22 to} R ₂₆ and R _{27 to} R ₃₁ in 3) are directly bonded to a hydrogen atom or a nitrogen atom in the general formula (1).

R _{1 to} R ₄ and R _{5 to} R _{9 in} the general formula (1-1), R _{10 to} R ₁₄ and R _{15 to} R ₁₉ in the general formula (1-2), and the general formula (1-). Examples of the organic groups that R _{22 to} R ₂₆ and R _{27 to} R ₃₁ in 3) can take include an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a cycloalkyl group having 3 to 8 carbon atoms. Examples thereof include a group, an aryl group having 6 to 12 carbon atoms, an allyl group, a trifluoromethyl group and the like.

Examples of the organic groups that R ₂₀ and R ₂₁ in the general formula (1-2) and R ₃₂ and R ₃₃ in the general formula (1-3) can take include alkyl groups having 1 to 3 carbon atoms. Examples thereof include an alkoxy group having 1 to 3 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, an allyl group, and a trifluoromethyl group.

Halogen that can be taken by R _{1 to} R ₉ in the general formula (1-1), R _{10 to} R ₂₁ in the general formula (1-2), and R _{22 to} R ₃₃ in the general formula (1-3). Examples of the atom include fluorine, chlorine and bromine. Of these, fluorine is preferable because of the permeability of the polymer.

R _{1 to} R ₉ in the general formula (1-1), R _{10 to} R ₂₁ in the general formula (1-2), and R _{22 to} R ₃₃ in the general formula (1-3) can be taken. Examples of the sulfonyl group include an alkylsulfonyl group having 1 to 10 carbon atoms such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, an octylsulfonyl group, a decylsulfonyl group and a dodecylsulfonyl group.

The alkali-soluble resin (A) is more preferably a polyamide resin having a benzoxazole skeleton in the main chain skeleton and having an imide precursor structure and a benzoxazole precursor structure. Such a polyamide resin is a polyamide resin which is a reaction product of an amine component and a carboxylic acid component, wherein the amine component is (a) a diamine component and (b) a dihydroxydiamine component, and the carboxylic acid component is (C) Tri or tetracarboxylic acid anhydride component and (d) Dicarboxylic acid component, (a) Diamine component, (b) Dihydroxydiamine component, (c) Tri or tetracarboxylic acid anhydride component and (d) A polyamide resin having at least one of the dicarboxylic acid components having a benzoxazole skeleton, having a benzoxazole skeleton in the main chain skeleton, and having an imide precursor structure and a benzoxazole precursor structure as a reactant is preferable. It is possible to obtain a photosensitive resin composition which can be used, is excellent in contrast, developability, development resistance of unexposed portion, dielectric property and strength of cured product, and can form a pattern having a higher taper angle. .. Further, when such a polyamide resin is contained, the deformation after curing is more remarkable, but according to the present invention, the deformation after curing is also suppressed. Further, the reaction between the amine component and the carboxylic acid component is not particularly limited as long as a polyamide resin can be obtained, and any reaction may be made as long as the amine component and the carboxylic acid component react to form an amide bond.

In the above-mentioned polyamide resin, (c) a tri or tetracarboxylic dianhydride component, which is one of the carboxylic acid components, forms an imide precursor structure by a double addition reaction with an amine component. Further, (b) dihydroxydiamine forms a benzoxazole precursor structure by a polycondensation reaction with a carboxylic acid component. That is, the polyamide resin is an imide precursor-benzoxazole precursor-amide copolymer addition condensation product. The polyamide resin may be a random copolymer in which the components (a) to (d) are reacted together, or the components (a) to (d) are sequentially reacted in any order. It may be a block copolymer.

The proportion of the imide precursor structure (that is, the amic acid structure) of the polyamide resin can be adjusted by the proportion of the (c) tri or tetracarboxylic dianhydride component in the carboxylic acid component. The ratio of the (c) tri or tetracarboxylic dianhydride component to 100 mol% of the carboxylic acid component is preferably 1 to 30 mol%, more preferably 1 to 15 mol%. (C) The carboxyl group equivalent of the polyamide resin derived from the tri or tetracarboxylic dianhydride component is preferably 1,000 or more, and more preferably 2,000 to 5,000.

The ratio of the benzoxazole precursor structure contained in the polyamide resin can be adjusted by the ratio of the (b) dihydroxydiamine component in the amine component. The ratio of the (b) dihydroxydiamine component to 100 mol% of the amine component is preferably 70 to 99 mol%, more preferably 80 to 99 mol%. Further, (b) the hydroxy group contained in the dihydroxydiamine component is preferably a phenolic hydroxyl group, and (b) the dihydroxydiamine component has a structure in which two hydroxy groups and two amino groups are located on the aromatic ring at the ortho position. It is more preferable to have. The phenolic hydroxyl group equivalent of the polyamide resin derived from such (b) dihydroxydiamine component is preferably 600 or less, and more preferably 100 to 300.

In the polyamide resin, (a) the diamine component preferably contains a diamine having a benzoxazole skeleton, and having the benzoxazole skeleton further improves heat resistance. The molar ratio of the diamine having a benzoxazole skeleton to the component (b) dihydroxydiamine is preferably 0.1: 99.9 to 30:70, preferably 0.1: 99.9 to 15:85. Is more preferable. When the (a) diamine has a benzoxazole skeleton, the molar ratio of the (c) tri or tetracarboxylic acid anhydride component and the (d) dicarboxylic acid component is 0.1: 99.9 to 30:70. It is preferably 0.1: 99.9 to 20:80, and more preferably 0.1: 99.9 to 20:80.

The diamine component (a) is not particularly limited, but in the present invention, the "(a) diamine component" does not include the "(b) dihydroxydiamine component". Examples of diamines in the case of aromatic groups are paraphenylenediamine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3. '-Dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 9,10-bis (4-aminophenyl) anthracene, 4,4'-diaminobenzophenone, 4, 4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfoxide, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) Phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxybiphenyl, bis [4- ( 4-Aminophenoxy) phenyl] ether, 1,1,1,3,3,3-hexafluoro-2,2-bis (4-aminophenyl) propane, 1,1,1,3,3,3-hexa Fluoro-2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3-amino-4-methylphenyl) Propane, metaphenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis ( 4-Aminophenoxy) benzene can be mentioned. Examples of the diamine in the case of an aliphatic group include 1,1-methaxylylene diamine, 1,3-propanediamine, tetramethylenediamine and pentamethylenediamine. , Hexamethylenediamine, Heptamethylenediamine, Octamethylenediamine, Nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, Isophoronediamine, Tetrahydrodicyclopentadienylene diamine, Hexahydro-4,7 -Metanoin daniylene methylenediamine, tricyclo [6.2.1.02,7] -undecylene dimethyldiamine, 4,4'-methylenebis (cyclohexylamine), isophoronediamine can be mentioned.

When the (a) diamine component has a benzoxazole skeleton, the (a) diamine component includes 6-amino-2- (4-aminophenyl) benzoxazole and 2- (4-aminophenyl) -5-aminobenzo. Diamines corresponding to the above-mentioned general formulas (1-1), (1-2) and (1-3) such as oxazole (that is, the above-mentioned general formulas (1-1), (1-2) and (1-3) ) Has two "direct bonds with the nitrogen atom in the general formula (1)" changed to an amino group).

As the diamine component (a), one type may be used alone, or two or more types may be used in combination. For example, as the diamine component (a), a diamine having a benzoxazole skeleton and a diamine not having a benzoxazole skeleton may be used in combination.

Examples of the dihydroxydiamine component (b) include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, and bis (3-amino-4-hydroxyphenyl). ) Propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3-) Amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3 Examples thereof include 3-hexafluoropropane. Of these, 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane is preferable. As the diamine diamine component (b), one type may be used alone, or two or more types may be used in combination.

Examples of the tricarboxylic acid anhydride component of (c) tri or tetracarboxylic acid anhydride include trimellitic acid anhydride and nuclear hydrogenated trimellitic acid anhydride. Examples of the tetracarboxylic acid dianhydride include pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3,6-difluoropyrimellitic dianhydride, and 3,6-bis (trifluoromethyl) pyromellitic acid. Dihydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic acid dianhydride , 2,2'-difluoro-3,3', 4,4'-biphenyltetracarboxylic dianhydride, 5,5'-difluoro-3,3', 4,4'-biphenyltetracarboxylic dianhydride , 6,6'-difluoro-3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 5,5', 6,6'-hexafluoro-3,3', 4 , 4'-biphenyltetracarboxylic dianhydride, 2,2'-bis (trifluoromethyl) -3,3', 4,4'-biphenyltetracarboxylic dianhydride, 5,5'-bis (tri) Fluoromethyl) -3,3', 4,4'-biphenyltetracarboxylic dianhydride, 6,6'-bis (trifluoromethyl) -3,3', 4,4'-biphenyltetracarboxylic dianhydride , 2,2', 5,5'-tetrakis (trifluoromethyl) -3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 6,6'-tetrakis (tri) Fluoromethyl) -3,3', 4,4'-biphenyltetracarboxylic dianhydride, 5,5', 6,6'-tetrakis (trifluoromethyl) -3,3', 4,4'-biphenyl Tetetracarboxylic dianhydride, and 2,2', 5,5', 6,6'-hexakis (trifluoromethyl) -3,3', 4,4'-biphenyltetracarboxylic dianhydride, 1, 2,3,4-benzenetetracarboxylic dianhydride, 3,3 ", 4,4"-terphenyltetracarboxylic dianhydride, 3,3'", 4,4'"-quaterphenyltetracarboxylic Acid dianhydride, 3,3 "", 4,4 ""-kinkphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic acid dianhydride, 1,1-ethylidene-4,4'- Diphthalic acid dianhydride, 2,2-propydian-4,4'-diphthalic acid dianhydride, 1,2-ethylene-4,4'-diphthalic acid dianhydride, 1,3-trimethylethylene-4,4' -Diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dian Anhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropanedianhydride (ie, 4,4'- (hexafluoroisopropyridene) ) Diphthalic acid anhydride), difluoromethylene-4,4'-diphthalic acid dianhydride, 1,1,2,2-tetrafluoro-1,2-ethylene-4,4'-diphthalic acid dianhydride, 1 , 1,2,2,3,3-hexafluoro-1,3-trimethylethylene-4,4'-diphthalic dianhydride, 1,1,2,2,3,3,4,5-octafluoro- 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,1,2,2,3,3,4,5,5-decafluoro-1,5-pentamethylene-4, 4'-diphthalic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis (3,4-dicarboxyphenyl)- 1,1,3,3-tetramethylsiloxane dianhydride, 1,3-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenyl) benzene dianhydride An anhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,3-bis [2- ( 3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, 1,4-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, bis [3- ( 3,4-dicarboxyphenoxy) phenyl] methane dianhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl] methaneni anhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) ) Penyl] propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl ] -1,1,1,3,3,3-hexafluoropropanedianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propanedianhydride, bis (3,4) -Dicarboxyphenoxy) Didimethylsilane dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) -1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7- Naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetra Carcarboxylic dianhydride, 2,3,6,7-anthranetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic acid Dihydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1, 2,4,5-tetracarboxylic dianhydride, 3,3', 4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) Dihydride, methylene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride , 1,1-Ethylenelidene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propanol-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) Dihydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4 '-Bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis (cyclohexane-) 1,2-dicarboxylic dianhydride) dianhydride, 3,3'-difluorooxy-4,4'-diphthalic dianhydride, 5,5'-difluorooxy-4,4'-diphthalic dianhydride, 6 , 6'-difluorooxy-4,4'-diphthalic dianhydride, 3,3', 5,5', 6,6'-hexafluorooxy-4,4'-diphthalic dianhydride, 3, 3'-bis (trifluoromethyl) oxy-4,4'-diphthalic dianhydride, 5,5'-bis (trifluoromethyl) oxy-4,4'-diphthalic dianhydride, 6,6' -Bis (trifluoromethyl) oxy-4,4'-diphthalic dianhydride, 3,3', 5,5'-tetrakis (trifluoromethyl) oxy-4,4'-diphthalic dianhydride, 3 , 3', 6,6'-tetrakis (trifluoromethyl) oxy-4,4'-diphthalic dianhydride, 5,5', 6,6'-tetrakis (trifluoromethyl) oxy-4,4' -Diphthalic dianhydride, 3,3', 5,5', 6,6'-hexakis (trifluoro) Methyl) Oxy-4,4'-diphthalic dianhydride, 3,3'-difluorosulfonyl-4,4'-diphthalic dianhydride, 5,5'-difluorosulfonyl-4,4'-diphthalic acid dianhydride Anhydride, 6,6'-difluorosulfonyl-4,4'-diphthalic dianhydride, 3,3', 5,5', 6,6'-hexafluorosulfonyl-4,4'-diphthalic dianhydride , 3,3'-bis (trifluoromethyl) sulfonyl-4,4'-diphthalic dianhydride, 5,5'-bis (trifluoromethyl) sulfonyl-4,4'-diphthalic dianhydride, 6,6'-bis (trifluoromethyl) sulfonyl-4,4'-diphthalic dianhydride, 3,3', 5,5'-tetrakis (trifluoromethyl) sulfonyl-4,4'-diphthalic acid dianhydride Anhydride, 3,3', 6,6'-tetrakis (trifluoromethyl) sulfonyl-4,4'-diphthalic dianhydride, 5,5', 6,6'-tetrakis (trifluoromethyl) sulfonyl- 4,4'-Diphthalic dianhydride, 3,3', 5,5', 6,6'-hexakis (trifluoromethyl) sulfonyl-4,4'-diphthalic dianhydride, 3,3'- Difluoro-2,2-perfluoropropydian-4,4'-diphthalic dianhydride, 5,5'-difluoro-2,2-perfluoropropydian-4,4'-diphthalic dianhydride, 6 , 6'-difluoro-2,2-perfluoropropydian-4,4'-diphthalic dianhydride, 3,3', 5,5', 6,6'-hexafluoro-2,2-perfluoro Propyridene-4,4'-diphthalic dianhydride, 3,3'-bis (trifluoromethyl) -2,2-perfluoropropydian-4,4'-diphthalic dianhydride, 5,5' -Bis (trifluoromethyl) -2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 6,6'-difluoro-2,2-perfluoropropydian-4,4'-diphthal Acid dianhydride, 3,3', 5,5'-tetrakis (trifluoromethyl) -2,2-perfluoropropydian-4,4'-diphthalic dianhydride, 3,3', 6,6 '-Tetrakis (trifluoromethyl) -2,2-perfluoropropydian-4,4'-diphthalic dianhydride, 5,5', 6,6'-tetrakis (trifluoromethyl) -2,2- Perfluoropropydian-4,4'-diphthalic dianhydride, 3,3', 5,5', 6,6'-hexakis (triflu) Oromethyl) -2,2-perfluoropropylidene-4,4'-diphthalic hydride, 9-phenyl-9- (trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic hydride , 9,9-bis (trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic hydride, bicyclo [2,2,2] octo-7-en-2,3,5,6- Tetracarboxylic acid dianhydride, 9,9-bis [4- (3,4-dicarboxy) phenyl] fluorene dianhydride, 9,9-bis [4- (2,3-dicarboxy) phenyl] fluorendi Anhydride, ethylene glycol bis trimellitate dianhydride, 1,2- (ethylene) bis (trimelitate anhydride), 1,3- (trimethylene) bis (trimelite anhydride), 1,4- (tetramethylene) bis ( (Trimeritate Anhydride), 1,5- (Pentamethylene) Bis (Trimeritate Anhydride), 1,6- (Hexamethylene) Bis (Trimeritate Anhydride), 1,7- (Heptamethylene) Bis (Trimeritate Anhydride), 1,8- (octamethylene) bis (trimeritate anhydride), 1,9- (nonamethylene) bis (trimeritate anhydride), 1,10- (decamethylene) bis (trimeritate anhydride), 1,12- (dodecamethylene) ) Bis (Trimeritate Anhydride), 1,16- (Hexadecamethylene) Bis (Trimeritate Anhydride), 1,18- (Octadecamethylene) Bis (Trimeritate Anhydride) and the like. As the (c) tri or tetracarboxylic dianhydride component, one type may be used alone, or two or more types may be used in combination.

Examples of the (d) dicarboxylic acid component include isophthalic acid, terephthalic acid, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, and 2,6-naphthalenedicarboxylic acid. 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2-bis (p-carboxyphenyl) propane , 2,2-Bis (4-carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane and other dicarboxylic acids with aromatic rings, oxalic acid, malonic acid, succinic acid, 1,2- Examples thereof include aliphatic dicarboxylic acids such as cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and 1,3-cyclopentanedicarboxylic acid, their dicarboxylic acid dihalides, and their dicarboxylic acid esters. Of these, 4,4'-dicarboxydiphenyl ether (that is, 4,4'-diphenyl ether dicarboxylic acid) and its dihalide are preferable. As the dicarboxylic acid component (d), one type may be used alone, or two or more types may be used in combination.

The polyamide resin is preferably a polyamide resin having a repeating structure represented by the following general formula (2) in which an amine component and a carboxylic acid component are amide-bonded.

（一般式（２）中、Ｘはアミン成分の残基であり、Ｙはカルボン酸成分の残基であり、前記アミン成分が、（ａ）ジアミン成分および（ｂ）ジヒドロキシジアミン成分であり、前記カルボン酸成分が、（ｃ）トリまたはテトラカルボン酸無水物成分と（ｄ）ジカルボン酸成分であり、前記（ａ）ジアミン成分、（ｂ）ジヒドロキシジアミン成分、（ｃ）トリまたはテトラカルボン酸無水物成分および（ｄ）ジカルボン酸成分の少なくともいずれか一種がベンゾオキサゾール骨格を有する。）

(In the general formula (2), X is a residue of an amine component, Y is a residue of a carboxylic acid component, and the amine component is (a) a diamine component and (b) a dihydroxydiamine component. The carboxylic acid component is (c) a tri or tetracarboxylic acid anhydride component and (d) a dicarboxylic acid component, and the (a) diamine component, (b) dihydroxydiamine component, (c) tri or tetracarboxylic acid anhydride. At least one of the component and (d) dicarboxylic acid component has a benzoxazole skeleton.)

In the general formula (2), X and the two nitrogen atoms on both sides thereof have a structure derived from an amine component, and Y and the two carbonyl groups on both sides thereof have a structure derived from a carboxylic acid component. In the general formula (2), (a) diamine component, (b) dihydroxydiamine component, (c) tri or tetracarboxylic acid anhydride component, and (d) dicarboxylic acid component are as described above.

In the general formula (2), the benzoxazole skeleton is the benzoxazole skeleton of any one of the general formulas (1-1), (1-2) and (1-3) (however, the "general formula" in the description of the formula. It is preferable that "in (1)" should be read as "in" in the general formula (2)).

In the general formula (2), (a) X derived from the diamine component and the two nitrogen atoms on both sides thereof have a structure represented by the following general formula (3).

（一般式（３）中、Ｚは（ａ）ジアミン成分の残基であり、２価の有機基である。）

(In the general formula (3), Z is a residue of the (a) diamine component and is a divalent organic group.)

In the general formula (3), the divalent organic group represented by Z may be an aliphatic group or an aromatic group, but is preferably an aromatic group. The number of carbon atoms of the divalent aromatic group is preferably 6 to 30, and more preferably 6 to 24.

In the general formula (3), the divalent organic group represented by Z is a benzoxazole skeleton according to any one of the general formulas (1-1), (1-2) and (1-3) (however, R _1). ~ R ₄ , R _{5 to} R ₉ , R _{10 to} R ₁₄ , R _{15 to} R ₁₉ , R _{22 to} R ₂₆ , and R _{27 to} R ₃₁ are all with the carbonyl group in the general formula (1). It is preferably a divalent group having (not a direct bond).

In the general formula (3), the diamine component represented by Z is a diamine corresponding to the general formulas (1-1), (1-2) and (1-3) (that is, the general formula (1-1). ), (1-2) and (1-3) have two "direct bonds with the nitrogen atom in the general formula (1)" modified to an amino group).

The ratio of the number of structures represented by the general formula (3) to 100 mol% of the structures derived from the amine component of the polyamide resin is preferably 1 to 40 mol%, and preferably 1 to 30 mol%. More preferred.

In the general formula (2), (b) X derived from the dihydroxydiamine component and the two nitrogen atoms on both sides thereof have a structure represented by the following general formula (4).

（一般式（４）中、Ｗは（ｂ）ジヒドロキシジアミン成分の残基であり、４価の有機基である。）

(In the general formula (4), W is a residue of the (b) dihydroxydiamine component and is a tetravalent organic group.)

In the general formula (4), the tetravalent organic group represented by W may be an aliphatic group or an aromatic group, but it is preferably an aromatic group, and two hydroxy groups and two amino groups are in the ortho position. It is more preferably located on the aromatic ring. The number of carbon atoms of the tetravalent aromatic group is preferably 6 to 30, and more preferably 6 to 24. Specific examples of the tetravalent aromatic group include, but are not limited to, known aromatic groups that can be contained in the polybenzoxazole precursor, depending on the intended use. Just do it.

The tetravalent aromatic group is preferably the following group among the aromatic groups.

The ratio of the number of structures represented by the above general formula (4) is preferably 60 to 99 mol%, preferably 70 to 99 mol%, per 100 mol% of the structures derived from the amine component of the polyamide resin. More preferred.

In the general formula (2), the Y derived from the tri or tetracarboxylic dianhydride component (c) and the two carbonyl groups on both sides thereof have a structure represented by the following general formula (5).

（一般式（５）中、Ｐは（ｃ）トリまたはテトラカルボン酸無水物成分の残基であり、３価または４価の有機基である。ｊは１または２である。）

(In the general formula (5), P is a residue of (c) a tri- or tetracarboxylic dianhydride component and is a trivalent or tetravalent organic group. J is 1 or 2.)

In the general formula (5), the trivalent or tetravalent organic group represented by P may be an aliphatic group or an aromatic group, but is preferably an aromatic group, and the general formula (5) is on the aromatic ring. It is more preferable that it is bonded to the carbonyl inside. The number of carbon atoms of the trivalent or tetravalent aromatic group is preferably 6 to 30, and more preferably 6 to 24. Specific examples of the trivalent or tetravalent aromatic group include, but are not limited to, a known aromatic group contained in the imide precursor can be selected according to the application. Just do it.

（式中、Ａは単結合、−ＣＨ_２−、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ_２−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、−Ｃ（ＣＨ_３）_２−からなる群から選択される２価の基を表す。）

(In the formula, A is a single bond, -CH _2- , -O-, -CO-, -S-, -SO _2- , -NHCO-, -C (CF ₃ ) _2- , -C (CH ₃ ). ₂ - represents a divalent radical selected from the group consisting of).

The trivalent or tetravalent organic group is preferably the following group among the aromatic groups.

The ratio of the number of structures represented by the above general formula (5) is preferably 1 to 50 mol%, preferably 1 to 15 mol%, per 100 mol% of the structures derived from the carboxylic acid component of the polyamide resin. Is more preferable.

In the general formula (2), the Y derived from the (d) dicarboxylic acid component and the two carbonyl groups on both sides thereof have a structure represented by the following general formula (6).

（一般式（６）中、Ｑは（ｄ）ジカルボン酸成分の残基であり、２価の有機基である。）

(In the general formula (6), Q is a residue of the (d) dicarboxylic acid component and is a divalent organic group.)

In the general formula (6), the divalent organic group represented by Q may be an aliphatic group or an aromatic group, but it is preferably an aromatic group, and the carbonyl in the general formula (6) on the aromatic ring. It is more preferable that it is combined with. The number of carbon atoms of the divalent aromatic group is preferably 6 to 30, and more preferably 6 to 24. Specific examples of the divalent aromatic group include, but are not limited to, a known aromatic group contained in the polybenzoxazole precursor can be selected according to the application. Good.

（式中、Ａは単結合、−ＣＨ_２−、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ_２−、−ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、−Ｃ（ＣＨ_３）_２−からなる群から選択される２価の基を表す。）

(In the formula, A is a single bond, -CH _2- , -O-, -CO-, -S-, -SO _2- , -NHCO-, -C (CF ₃ ) _2- , -C (CH ₃ ). ₂ - represents a divalent radical selected from the group consisting of).

The divalent organic group is preferably the following group among the aromatic groups.

The ratio of the number of structures represented by the general formula (6) to 100 mol% of the structures derived from the carboxylic acid component of the polyamide resin is preferably 50 to 99 mol%, and is 85 to 99 mol%. Is more preferable.

Examples of the repeating unit of the amide structure contained in the polyamide resin include structural units represented by the following general formulas (7) to (10).

The structural unit represented by the following general formula (7) is a structural unit derived from (a) a diamine component and (c) a tri or tetracarboxylic dianhydride component.

（一般式（７）中、Ｚは一般式（３）と同様であり、Ｐおよびｊは一般式（５）と同様である。）

(In the general formula (7), Z is the same as the general formula (3), and P and j are the same as the general formula (5).)

As a specific example of the structural unit represented by the general formula (7), for example, (a) the diamine component is 6-amino-2- (4-aminophenyl) benzoxazole, and (c) a tri or tetracarboxylic acid. Examples thereof include, but are not limited to, the following structural units in which the anhydride component is 4,4'-(hexafluoroisopropyridene) diphthalic anhydride.

（右側の４，４’−（ヘキサフルオロイソプロピリデン）ジフタル酸無水物（６ＦＤＡ）由来の構造において、アミド結合およびカルボキシル基はメタ位またはパラ位である。）

(In the structure derived from 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) on the right side, the amide bond and the carboxyl group are in the meta or para position.)

The structural unit represented by the following general formula (8) is a structural unit derived from (a) a diamine component and (d) a dicarboxylic acid component.

（一般式（８）中、Ｚは一般式（３）と同様であり、Ｑは一般式（６）と同様である。）

(In the general formula (8), Z is the same as the general formula (3), and Q is the same as the general formula (6).)

As a specific example of the structural unit represented by the general formula (8), for example, (a) the diamine component is 6-amino-2- (4-aminophenyl) benzoxazole, and (d) the dicarboxylic acid component is. The following structural units, which are 4,4'-diphenyl ether dicarboxylic acid chloride, can be mentioned, but are not limited thereto.

The structural unit represented by the following general formula (9) is a structural unit derived from (b) a dihydroxydiamine component and (c) a tri or tetracarboxylic dianhydride component.

（一般式（９）中、Ｗは一般式（４）と同様であり、Ｐおよびｊは一般式（５）と同様である。）

(In the general formula (9), W is the same as the general formula (4), and P and j are the same as the general formula (5).)

As a specific example of the structural unit represented by the general formula (9), for example, (b) the dihydroxydiamine component is bis (3-amino-4-hydroxyamidephenyl) hexafluoropropane, and (c) tri or tri or Examples thereof include, but are not limited to, the following structural units in which the tetracarboxylic dianhydride component is 4,4'-(hexafluoroisopropyridene) diphthalic anhydride.

（右側の４，４’−（ヘキサフルオロイソプロピリデン）ジフタル酸無水物（６ＦＤＡ）由来の構造において、アミド結合およびカルボキシル基はメタ位またはパラ位である。）

(In the structure derived from 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) on the right side, the amide bond and the carboxyl group are in the meta or para position.)

The structural unit represented by the following general formula (10) is a structural unit derived from (b) a dihydroxydiamine component and (d) a dicarboxylic acid component.

（一般式（１０）中、Ｗは一般式（４）と同様であり、Ｑは一般式（６）と同様である。）

(In the general formula (10), W is the same as the general formula (4), and Q is the same as the general formula (6).)

As a specific example of the structural unit represented by the general formula (10), for example, (b) the dihydroxydiamine component is bis (3-amino-4-hydroxyamidephenyl) hexafluoropropane, and (d) a dicarboxylic acid. Examples thereof include, but are not limited to, the following structural units in which the component is 4,4'-diphenyl ether dicarboxylic acid chloride.

Further, as an example of the alkali-soluble resin (A), a polyamide resin having no imide precursor structure, having a benzoxazole skeleton in the main chain skeleton, and having a benzoxazole precursor structure can be mentioned. Such a polyamide resin is a polyamide resin which is a reaction product of an amine component and a carboxylic acid component, wherein the amine component is (a) a diamine component and (b) a dihydroxydiamine component, and the carboxylic acid component is (D) A dicarboxylic acid component, at least one of the (a) diamine component, (b) dihydroxydiamine component and (d) dicarboxylic acid component has a benzoxazole skeleton, and a benzoxazole skeleton is used as a reaction product. A polyamide resin having a main chain skeleton and having a benzoxazole precursor structure can be preferably used. The same applies to the (a) diamine component, (b) dihydroxydiamine component and (d) dicarboxylic acid component. Further, such a polyamide resin has a repeating structure represented by the above general formula (2) in which an amine component and a carboxylic acid component are amide-bonded (however, "the carboxylic acid component is (c) tri or tetra. "The carboxylic acid anhydride component and (d) dicarboxylic acid component" is preferably a polyamide resin having "the carboxylic acid component is (d) a dicarboxylic acid component"). Here, the same applies to the general formulas (3), (4) and (6), but the structure represented by the general formula (6) is per 100 mol% of the structure derived from the carboxylic acid component of the polyamide resin. The proportion of numbers is 100 mol%.

The number average molecular weight (Mn) of the alkali-soluble resin (A) is preferably 3,000 to 100,000, and more preferably 5,000 to 50,000. Here, the number average molecular weight is a numerical value measured by gel permeation chromatography (GPC) and converted with standard polystyrene. The weight average molecular weight (Mw) of the polyamide resin of the present invention is preferably 6,000 to 200,000, more preferably 15,000 to 100,000. Here, the weight average molecular weight is a numerical value measured by GPC and converted by standard polystyrene. Mw / Mn is preferably 1 to 6, and more preferably 1 to 4.

As the alkali-soluble resin (A), one type may be used alone, or two or more types may be used in combination. The blending amount of the alkali-soluble resin (A) is preferably 5 to 90% based on the total solid content of the composition.

The positive photosensitive resin composition of the present invention may contain an alkali-soluble resin other than the (A) alkali-soluble resin as long as the effects of the present invention are not impaired.

[(B) Photosensitizer]
(B) Examples of the photosensitizer include naphthoquinone diazide compounds, diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, and nitrobenzyl Examples thereof include photoacid generators such as esters, aromatic N-oxyimide sulfonates, aromatic sulfamides, and benzoquinone diazosulfonic acid esters. (B) The photosensitizer is preferably a dissolution inhibitor. Of these, it is preferably a naphthoquinone diazide compound.

Specific examples of the naphthoquinone diazide compound include naphthoquinone diazide adducts of tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene (for example, TKF-520 and TKF-528 manufactured by Sanpo Chemical Research Institute). , TKF-420, TKF-428), naphthoquinone diazide adduct of tetrahydroxybenzophenone (for example, BS550, BS570, BS599 manufactured by Sanpo Chemical Laboratory Co., Ltd.) and the like can be used. Here, the addition of naphthoquinone diazide may be carried out, for example, by reacting o-quinone diazidosulfonyl chlorides with a hydroxy compound or an amino compound.

(B) As the photosensitizer, one type may be used alone, or two or more types may be used in combination. The amount of the photosensitizer (B) is preferably 3 to 20% by mass based on the total solid content of the composition.

[(C) Filler with an average particle size of 2 μm or less]
As the filler (C), the filler may be an organic filler or an inorganic filler, but an inorganic filler is preferable. Examples of the inorganic filler include silica, barium sulfate, barium titanate, Neuburg silica soil, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, titanium oxide, aluminum hydroxide, silicon nitride, and aluminum nitride. Of these, silica is preferable. Examples of silica include fused silica, spherical silica, amorphous silica, and crystalline silica.

The average particle size of the filler (C) is preferably 0.01 to 2 μm, more preferably 0.05 to 1.5 μm. Further, from the viewpoint of the formability of a high taper angle, the average particle size of the filler (C) is more preferably 0.4 μm or less. Here, in the present specification, the average particle size of the filler is the average particle size (D50) including not only the particle size of the primary particles but also the particle size of the secondary particles (aggregates), and is determined by the laser diffraction method. It is a measured value of D50. Further, as a measuring device by a laser diffraction method, a Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. can be mentioned.

The filler (C) is preferably a filler surface-treated with a surface treatment agent. As the surface treatment agent, a coupling agent is preferable. As the coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent and the like can be used. Of these, a silane coupling agent is preferable, and after being dispersed in the liquid, precipitation and aggregation can be prevented, and as a result, storage stability is more excellent. In addition, even when the composition is blended, it can be stably charged without agglomeration. Further, the wettability of the obtained cured product resin and the filler can be improved. One type of surface treatment agent may be used alone, or two or more types may be used in combination.

The surface treatment agent may have an organic group, and examples of such an organic group include a methacryl group, an acrylic group, a vinyl group, a styryl group, a phenyl group, an epoxy group, an amino group, a hydroxyl group, a carboxyl group and an isocyanate. Examples thereof include a group, imino group, oxetanyl group, mercapto group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, ethoxyethyl group, oxazoline group and the like.

The filler (C) is preferably spherical silica surface-treated with a surface treatment agent having at least one of a phenyl group, an epoxy group, an aminophenyl group and a vinyl group, and is well mixed with varnish and aggregates. Is suppressed and the resolution is improved. Further, an epoxy group and a vinyl group are more preferable from the viewpoint of stackability, and a phenyl group is more preferable from the viewpoint of storage stability. The shape of the spherical silica may be spherical, and is not limited to that of a true spherical silica. Suitable spherical silicas include, but are not limited to, those having a sphericity of 0.8 or more as measured as follows.
The sphericity is measured as follows. A photograph is taken by SEM, and it is calculated as a value calculated by (sphericity) = {4π × (area) ÷ (peripheral length) ² } from the observed particle area and peripheral length. Specifically, the average value measured for 100 particles using an image processing device is adopted.

(C) When the filler is surface-treated with a surface treatment agent, it is sufficient that the filler is blended in the positive photosensitive resin composition of the present invention in the surface-treated state, and the surface-untreated filler and the surface treatment agent are separately separated. Although the filler may be surface-treated in the composition by blending with, it is preferable to blend the filler which has been surface-treated in advance. By blending the filler that has been surface-treated in advance, it is possible to prevent deterioration of crack resistance and the like due to the surface treatment agent that may remain when the fillers are blended separately and are not consumed in the surface treatment. When surface-treating in advance, it is preferable to mix a pre-dispersion solution in which the filler (C) is pre-dispersed in a solvent or a resin component, and the surface-treated filler is pre-dispersed in a solvent and the pre-dispersion solution is blended in the composition. It is more preferable to add the pre-dispersion solution to the composition after sufficient surface treatment when the surface-untreated filler is pre-dispersed in the solvent.

The solvent is not particularly limited, but cyclohexanone is preferable, and aggregation of fillers (so-called solvent shock) caused by affinity with an alkali-soluble resin or other solvent is suppressed, making it easier to achieve both a high taper angle and stackability. Become.

As the filler (C), one type may be used alone, or two or more types may be used in combination. The blending amount of the filler (C) is preferably 2 to 50% based on the total solid content of the composition.

(Self-polymerizable compound)
The positive photosensitive resin composition of the present invention preferably contains a self-polymerizable compound, and has better stackability. The self-polymerizable compound in the present invention is a compound that polymerizes by itself due to heat or the like to increase the molecular weight. The self-polymerizable compound is not particularly limited as long as it is a compound having two or more self-polymerizable functional groups, and examples thereof include a phenol compound, a compound having a methylol group, a (meth) acrylic compound, a vinyl compound, and an epoxy compound. Be done. Of these, (meth) acrylic compounds and epoxy compounds are preferable, and epoxy compounds are more preferable from the viewpoint of stackability.

The (meth) acrylic compound is not particularly limited as long as it is a compound having a (meth) acryloyl group, but a compound having two compounds having a (meth) acryloyl group is preferable, and among them, a diol (ethylene oxide or propylene oxide) is preferable. Di (meth) acrylate of an alkylene oxide adduct (such as) or bifunctional polyester (meth) acrylate is preferable, and bifunctional polyester (meth) acrylate is more preferable. In addition, in this specification, (meth) acrylic compound is a generic term for an acrylic compound, a methacrylic compound and a mixture thereof, and the same applies to other similar expressions.

As the di (meth) acrylate of the alkylene oxide adduct of the diol, specifically, the diol is preferably alkylene oxide-modified and then the (meth) acrylate is added to the terminal, and the diol having an aromatic ring is more preferable. .. For example, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A PO (propylene oxide) adduct diacrylate and the like can be mentioned. The specific structure of the di (meth) acrylate of the alkylene oxide adduct of the diol is shown below, but is not limited thereto.

（式中、ｍ＋ｎは２以上であり、２〜４０であることが好ましく、３．５〜２５であることがより好ましい。）

(In the formula, m + n is 2 or more, preferably 2 to 40, and more preferably 3.5 to 25).

As the bifunctional polyester (meth) acrylate, M-6200, M-6250, and M-6500 (trade name manufactured by Toagosei Co., Ltd.) are preferable.

Bifunctional or higher functional epoxy compounds include epoxidized vegetable oils; bisphenol A type epoxy compounds; hydroquinone type epoxy compounds; bisphenol type epoxy compounds; thioether type epoxy compounds; brominated epoxy compounds; novolac type epoxy compounds; biphenol novolac type epoxy compounds; Bisphenol F type epoxy compound; hydrogenated bisphenol A type epoxy compound; glycidylamine type epoxy compound; hydantin type epoxy compound; alicyclic epoxy compound; trihydroxyphenylmethane type epoxy compound; bixylenel type or biphenol type epoxy compound or their Mixtures; bisphenol S-type epoxy compounds; bisphenol A novolac-type epoxy compounds; tetraphenylol ethane-type epoxy compounds; heterocyclic epoxy compounds; diglycidyl phthalate compounds; tetraglycidyl xylenoyl ethane compounds; epoxy compounds having a naphthalene skeleton; Epoxy compounds having a cyclopentadiene skeleton; glycidyl methacrylate copolymerized epoxy compounds; cyclohexyl maleimide and glycidyl methacrylate copolymerized epoxy compounds; epoxy-modified polybutadiene rubber derivatives; CTBN-modified epoxy compounds and the like, but are limited thereto. It's not a thing. The bifunctional or higher functional epoxy compound is preferably a bifunctional epoxy compound.

The blending amount of the self-polymerizing compound is preferably 1 to 100 parts by mass, more preferably 2 to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A).

(Sensitizer, adhesive, other ingredients)
The positive photosensitive resin composition of the present invention includes a known sensitizer for further improving the photosensitivity and silane coupling for improving the adhesiveness with the substrate, as long as the effect of the present invention is not impaired. It is also possible to blend a known adhesive such as an agent. Further, in order to impart processing characteristics and various functionalities to the positive photosensitive resin composition of the present invention, various other organic or inorganic low molecular weight or high molecular weight compounds may be blended. For example, a surfactant, a leveling agent, fine particles and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, and inorganic fine particles such as silica, carbon and layered silicate. Further, various colorants, fibers, plasticizers, thermal acid generators and the like may be blended with the positive photosensitive resin composition of the present invention.

(solvent)
The solvent used in the positive photosensitive resin composition of the present invention is not particularly limited as long as it dissolves (A) an alkali-soluble resin, (B) a photosensitive agent, and other additives. As an example, N, N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N, N'-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ- Butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, dimethylsulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone, diethylene glycol monomethyl ether can be mentioned. These may be used alone or in combination of two or more. Further, as described above, it is preferable to contain cyclohexanone as a solvent. The amount of solvent used can be appropriately determined according to the coating film thickness and viscosity. For example, it can be used in the range of 50 to 9,000 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (A). When cyclohexanone is contained as a solvent, it is more preferable to contain 0.1 to 50% by mass in the positive photosensitive resin composition.

[Dry film]
The dry film of the present invention has a resin layer obtained by applying the positive photosensitive resin composition of the present invention and then drying it.

The dry film of the present invention is dried by uniformly applying the positive photosensitive resin composition of the present invention to a carrier film (support film) by an appropriate method using a blade coater, a lip coater, a comma coater, a film coater, or the like. Then, the above-mentioned resin layer is formed, and preferably, a cover film (protective film) is laminated on the resin layer. The cover film and the carrier film may be the same film material or different films may be used.

In the dry film of the present invention, as the film material of the carrier film and the cover film, any known one as used for the dry film can be used.

As the carrier film, for example, a thermoplastic film such as a polyester film such as polyethylene terephthalate having a thickness of 2 to 150 μm is used.

As the cover film, a polyethylene film, a polypropylene film or the like can be used, but one having a smaller adhesive force with the resin layer than the carrier film is preferable.

The film thickness of the resin layer on the dry film of the present invention is preferably 100 μm or less, more preferably 5 to 50 μm.

Using the positive photosensitive resin composition of the present invention, the pattern film which is a cured product thereof may be produced by a known and commonly used production method, and is produced, for example, by the following steps.

First, as step 1, a coating film is obtained by applying and drying a positive photosensitive resin composition on a substrate, or by transferring (laminating) a resin layer from a dry film onto a substrate. As a method of applying the positive photosensitive resin composition on the substrate, methods conventionally used for coating the photosensitive resin composition, for example, spin coater, bar coater, blade coater, curtain coater, screen printing A method of applying by a machine or the like, a method of applying by spraying with a spray coater, an inkjet method or the like can be used. As a method for drying the coating film, a method such as air drying, heat drying using an oven or a hot plate, and vacuum drying is used. Further, it is desirable that the coating film is dried under conditions that do not cause ring closure of the alkali-soluble resin (A) in the positive photosensitive resin composition. Specifically, natural drying, blast drying, or heat drying can be performed at 70 to 140 ° C. for 1 to 30 minutes. Preferably, it is dried on a hot plate for 1 to 20 minutes. Vacuum drying is also possible, and in this case, it can be performed at room temperature for 20 minutes to 1 hour.

The base material on which the coating film of the positive photosensitive resin composition is formed is not particularly limited, and can be widely applied to semiconductor base materials such as silicon wafers, wiring boards, and base materials made of various resins and metals.

Next, as step 2, the coating film is exposed through a photomask having a pattern or directly. The exposure light has a wavelength that can activate the photosensitizer and generate an acid. Specifically, the exposed light beam preferably has a maximum wavelength in the range of 350 to 410 nm. As described above, the photosensitizer can be adjusted by appropriately blending the sensitizer. As the exposure apparatus, a contact aligner, a mirror projection, a stepper, a laser direct exposure apparatus and the like can be used.

Subsequently, as step 3, a part of the alkali-soluble resin (A) in the unexposed portion may be cyclized by heating. Here, the cyclization rate is about 30%. The heating time and heating temperature are appropriately changed depending on the polyamide resin, the coating film thickness, and the type of the photosensitizer as the photosensitizer.

Then, as step 4, the coating film is treated with a developer. As a result, the exposed portion in the coating film can be removed to form a pattern film of the positive photosensitive resin composition of the present invention.

As a method used for development, any method can be selected from conventionally known photoresist developing methods, such as a rotary spray method, a paddle method, and a dipping method accompanied by ultrasonic treatment. The developing solution includes inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine and triethanolamine, tetramethylammonium hydroxide and tetrabutylammonium hydroxide. Examples thereof include aqueous solutions of quaternary ammonium salts and the like. Further, if necessary, a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol or a surfactant may be added in an appropriate amount. Then, if necessary, the coating film is washed with a rinsing solution to obtain a patterned film. As the rinsing solution, distilled water, methanol, ethanol, isopropyl alcohol and the like can be used alone or in combination. Moreover, you may use the said solvent as a developer.

Then, as step 5, the pattern film is heated to obtain a cured coating film (cured product). At this time, the precursor structure of the alkali-soluble resin (A) is cyclized to obtain a benzoxazole skeleton and an imide skeleton. The heating temperature is appropriately set so that the pattern film of the photosensitive resin composition can be cured. For example, heating is carried out in an inert gas at 150 ° C. or higher and lower than 350 ° C. for about 5 to 120 minutes. A more preferred range of heating temperature is 180-320 ° C. Heating is performed, for example, by using a hot plate, an oven, or a heating oven in which a temperature program can be set. As the atmosphere (gas) at this time, air may be used, or an inert gas such as nitrogen or argon may be used.

The use of the positive photosensitive resin composition of the present invention is not particularly limited, and for example, as a paint, a printing ink, or an adhesive, or as a material for forming a display device, a semiconductor device, an electronic component, an optical component, or a building material. It is preferably used. Specifically, the display device can be used as a layer-forming material or an image-forming material for a color filter, a film for a flexible display, a resist material, an alignment film, or the like. Further, as a material for forming a semiconductor device, it can be used as a resist material, a layer forming material such as a buffer coat film, or the like. Further, as a material for forming an electronic component, it can be used as a sealing material or a layer forming material for a printed wiring board, an interlayer insulating film, a wiring coating film, or the like. Furthermore, as an optical component forming material, an optical material or a layer forming material can be used for holograms, optical waveguides, optical circuits, optical circuit components, antireflection films and the like. Furthermore, as a building material, it can be used as a paint, a coating agent, or the like.

The positive photosensitive resin composition of the present invention is mainly used as a pattern forming material, and the pattern film formed thereby is heat resistant and insulated as, for example, a permanent film composed of a polymer having a benzoxazole skeleton and an imide skeleton. Since it functions as a component that imparts properties, it particularly protects surface protective films for semiconductor devices, display devices and light emitting devices, interlayer insulating films, insulating films for rewiring, protective films for flip chip devices, and devices with bump structures. It can be suitably used as a film, an interlayer insulating film for a multilayer circuit, an insulating material for passive components, a protective film for a printed wiring board such as a solder resist or a coverlay film, and a liquid crystal alignment film. In particular, it is suitable for use as an insulating film in contact with copper wiring or aluminum wiring.

The positive photosensitive resin composition of the present invention can be suitably used as a material for forming a laminated electronic component. Examples of the laminated electronic component include a laminated electronic component used in various electronic devices such as digital devices, AV devices, and information communication terminals, and examples thereof include passive components such as inductors and active components (note that). , In the present specification, the concept of "laminated electronic component" does not include a printed wiring board). As the laminated electronic component, the electrode layer and the insulating layer which is a cured product of the positive photosensitive resin composition of the present invention are alternately laminated, and the electrode layer is formed in a coil shape as a whole. Can be mentioned. The laminated electronic component is preferably an inductor.

The thickness of the insulating layer is preferably 1 to 500 μm.

The electrode layer preferably has a thickness of 50 μm or less, and more preferably 15 μm or less. The electrode layer is not particularly limited as long as it has conductivity such as a silver (Ag) material or a copper (Cu) material, but it is more preferable to use a circuit formed of copper. Further, in the case of a paste such as copper paste or silver paste, it is formed by a screen printing method or the like, and another method such as copper foil etching, copper plating or a coil lead wire is used. It is also good and is not particularly limited.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. In the following, "part" and "%" are all based on mass unless otherwise specified.

((A) Synthesis of alkali-soluble resin)
(Synthesis Example 1: Alkali-soluble polyamide resin A1 (polyamide resin having a benzoxazole precursor structure))
72 g of N-methylpyrrolidone (NMP) was charged in a 0.5 liter flask equipped with a stirrer and a thermometer, and 8.50 g (23.2 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP) was charged. And 6-amino-2- (4-aminophenyl) benzoxazole (O-BO) 0.581 g (2.58 mmol) were stirred and dissolved. Immerse the flask in an ice bath and add 8.30 g (28.1 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride (DEDC) as a solid over 2 minutes while keeping the temperature inside the flask at 0 to 15 ° C. It was stirred in for 30 minutes. The ice bath was removed and stirring was continued at room temperature for 18 hours. The stirred solution was poured into 400 mL of ion-exchanged water to recover the precipitate. Then, the obtained solid was dissolved in 420 mL of acetone and put into 1 L of ion-exchanged water. After recovering the precipitated solid, it was dried under reduced pressure to obtain an alkali-soluble benzoxazole precursor structure-benzoxazole skeleton copolymerized polyamide resin A1 at the terminal of the carboxyl group. The weight average molecular weight determined by GPC method standard polystyrene conversion was 31,400.

カルボン酸成分：

(Amine component and carboxylic acid component used in Synthesis Example 1)
Amine component:

Carboxylic acid component:

(Repeat structure of alkali-soluble polyamide resin A1)

(Synthesis Example 2: Alkali-soluble polyamide resin A2 (polyamide resin having an imide precursor structure and a benzoxazole precursor structure))
70 g of N-methylpyrrolidone was placed in a 0.5 liter flask equipped with a stirrer and a thermometer, and 8.50 g (23.2 mmol) of bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP) and 2- 0.581 g (2.58 mmol) of (4-aminophenyl) -5-aminobenzoxazole (N-BO) was dissolved by stirring. Then, the flask was immersed in an ice bath, and 7.46 g (25.3 mmol) of 4,4'-diphenyl ether dicarboxylic acid chloride (DEDC) was added as a solid over 10 minutes while keeping the temperature inside the flask at 0 to 5 ° C. The mixture was stirred in an ice bath for 15 minutes. Subsequently, 1.25 g (2.81 mmol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) was added as a solid, and the mixture was stirred in an ice bath for 30 minutes. Then, stirring was continued for 18 hours at room temperature. The stirred solution was put into 400 mL of ion-exchanged water (specific resistance value 18.2 MΩ · cm), and the precipitate was recovered. Then, the obtained solid was dissolved in 420 mL of acetone and put into 1 L of ion-exchanged water. After recovering the precipitated solid, it was dried under reduced pressure to obtain an alkali-soluble benzoxazole skeleton-amic acid structure copolymer amide resin A2 at the terminal of the carboxyl group. The weight average molecular weight determined by GPC method standard polystyrene conversion was 31,400.

カルボン酸成分：

(Amine component and carboxylic acid component used in Synthesis Example 2)
Amine component:

Carboxylic acid component:

（右側の４，４’−（ヘキサフルオロイソプロピリデン）ジフタル酸無水物（６ＦＤＡ）由来の構造において、アミド結合およびカルボキシル基はメタ位またはパラ位である。）

（右側の４，４’−（ヘキサフルオロイソプロピリデン）ジフタル酸無水物（６ＦＤＡ）由来の構造において、アミド結合およびカルボキシル基はメタ位またはパラ位である。）

(Repeat structure of alkali-soluble polyamide resin A2)

(In the structure derived from 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) on the right side, the amide bond and the carboxyl group are in the meta or para position.)

(In the structure derived from 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) on the right side, the amide bond and the carboxyl group are in the meta or para position.)

(Preparation of positive photosensitive resin composition)
After adding γ-butyrolactone to the alkali-soluble resin so as to be 30% by mass of the non-volatile component and completely dissolving it, add each component at the ratio shown in Table 1 below (the numerical values in the table are parts by mass as the non-volatile component). , Stirred.

(Evaluation of stackability)
The varnish of the positive photosensitive resin composition was spin-coated on a silicon wafer and heated at 120 ° C. for 4 minutes to form a coating film having a film thickness of 30 μm. Then, the coating film was heated in an inert gas oven at 120 ° C. for 15 minutes in a nitrogen atmosphere, then heated at 4 ° C./min and heated at 220 ° C. for 60 minutes to obtain a cured film having a film thickness of 20 μm. On the obtained sample, the sample was applied again on the cured film and cured at 220 ° C. for 60 minutes.
By repeating this operation, those that could be laminated 6 times or more without cracks were ◎, those that could be laminated 3 to 5 times were ○, those that could be laminated twice were △, and those that were laminated less than 2 times were cracked. It was marked as x.

(Evaluation of storage stability)
The varnishes left at room temperature for 3 days and the varnishes left for 1 month were measured for viscosity, and those with a change in viscosity value of 5% or less were ◎, those with a viscosity value of more than 5% and within 10% were ○, and those with a change of more than 10% were within 30%. Was defined as Δ, and over 30% was defined as ×.

(Evaluation of deformation after curing and measurement of taper angle)
The varnish of the positive photosensitive resin composition was applied onto a silicon substrate subjected to copper sputtering using a spin coater. It was dried on a hot plate at 120 ° C. for 3 minutes to obtain a dry film having a thickness of 18 μm of the positive photosensitive resin composition. The obtained dry film was irradiated with i-rays of 1000 mJ / cm ² using a high-pressure mercury lamp through a mask on which a pattern was engraved. After exposure, it was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 80 seconds and rinsed with water to obtain a positive pattern. A similar test was performed on a silicon wafer.
A line pattern was observed using a scanning electron microscope (JSM-610 manufactured by JEOL), the pattern was confirmed after curing, and the taper angle after development was measured.
Those without pattern deformation after curing were marked with ◯, and those with some were marked with x.
A taper angle of 80 ° or more was evaluated as ⊚, a taper angle of less than 80 ° and 70 ° or more was evaluated as ◯, and a taper angle of less than 70 ° was evaluated as x.

<Photosensitizer B1>
Naftquinone diazide compound (TKF-428 manufactured by Sanpo Chemical Research Institute)

<(C) Filler>
(C1)
Cyclohexanone dispersion of spherical silica with an average particle diameter of 500 nm treated with a surface treatment agent having an aminophenyl group (removal of coarse particles of 5 μm or more, 30% by mass of non-volatile component, manufactured by Admatex, the amount in the table is the solid content)
(C2)
Cyclohexanone-dispersed product of spherical silica with an average particle diameter of 500 nm treated with a surface treatment agent having an epoxy group (removal of coarse particles of 5 μm or more, 30% by mass of non-volatile component, manufactured by Admatex, the amount in the table is the amount of solid content)
(C3)
Cyclohexanone-dispersed product of spherical silica with an average particle diameter of 500 nm treated with a surface treatment agent having a phenyl group (removal of coarse particles of 5 μm or more, 30% by mass of non-volatile component, manufactured by Admatex, amounts in the table are solid contents)
(C4)
Cyclohexanone-dispersed product of spherical silica with an average particle diameter of 500 nm treated with a surface treatment agent having a vinyl group (removal of coarse particles of 5 μm or more, non-volatile component 30% by mass, manufactured by Admatex, the amount in the table is the amount of solid content)
(C5)
N-methylpyrrolidone dispersion of spherical silica with an average particle size of 300 nm surface-treated with a surface treatment agent having an aminophenyl group (removal of coarse particles of 5 μm or more, 30% by mass of non-volatile component, manufactured by Admatex, the amount in the table is Solid content)
(C6)
N-methylpyrrolidone dispersion of spherical silica with an average particle size of 300 nm surface-treated with a surface treatment agent having an epoxy group (removal of coarse particles of 5 μm or more, non-volatile component 30% by mass, manufactured by Admatex, the amount in the table is solid Quantity)

<Self-polymerizable compound>
(D1) EPICLON-860 manufactured by DIC Corporation

From the results shown in the above table, the positive photosensitive resin composition of the present invention has excellent storage stability, is capable of forming a pattern with a high taper angle, and is not cracked by a solvent or deformed during thermosetting. It can be seen that the positive photosensitive resin composition is suitable for forming a laminated structure.

Claims (7)

(A) An alkali-soluble resin containing at least one of a benzoxazole precursor structure and an imide precursor structure as a repeating unit.
(B) Photosensitizer and
(C) Filler with an average particle size of 2 μm or less,
A positive photosensitive resin composition comprising. The positive photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) contains a benzoxazole skeleton. The second aspect of claim 2, wherein the alkali-soluble resin (A) is a polyamide resin which is a reaction product of an amine component and a carboxylic acid component, and has a repeating unit represented by the following general formula (1). Positive type photosensitive resin composition.

(In the general formula (1), U is a divalent organic group which is a residue of an amine component, R'is a divalent organic group which is a residue of a carboxylic acid component, and at least U and R'. One of them is a divalent organic group having a benzoxazole skeleton according to any one of the following general formulas (1-1), (1-2) and (1-3).

(In the general formula (1-1), R _{1 to} R ₄ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a nitrogen atom or a carbonyl in the general formula (1). It is either a direct bond with a group and may be the same or different. R _{5 to} R ₉ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, or , It is either a direct bond with a nitrogen atom or a carbonyl group in the general formula (1), and may be the same or different. However, any one of R _{1 to} R ₄ and Any one of R _{5 to} R ₉ is either a direct bond with a nitrogen atom in the general formula (1) or a direct bond with a carbonyl group in the general formula (1).)

(In the general formula (1-2), R _{10 to} R ₁₄ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a nitrogen atom or a carbonyl in the general formula (1). It is either a direct bond with a group and may be the same or different. R _{15 to} R ₁₉ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, or , It is either a direct bond with a nitrogen atom or a carbonyl group in the general formula (1), and may be the same or different. However, any one of R _{10 to} R ₁₄ and Any one of R _{15 to} R ₁₉ is either a direct bond with the nitrogen atom in the general formula (1) or a direct bond with the carbonyl group in the general formula (1). R ₂₀ , R ₂₁ is any one of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, and an amino group, and may be the same or different.)

(In the general formula (1-3), R _{22 to} R ₂₆ are a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, an amino group, or a nitrogen atom or a carbonyl in the general formula (1). It is either a direct bond with a group and may be the same or different. R _27- R ₃₁ are hydrogen atoms, organic groups, nitro groups, halogen atoms, sulfo groups, sulfonyl groups, amino groups, or , It is either a direct bond with a nitrogen atom or a carbonyl group in the general formula (1), and may be the same or different. However, any one of R _{22 to} R ₂₆ , and Any one of R _{27 to} R ₃₁ is either a direct bond with the nitrogen atom in the general formula (1) or a direct bond with the carbonyl group in the general formula (1). R ₃₂ , R ₃₃ is any one of a hydrogen atom, an organic group, a nitro group, a halogen atom, a sulfo group, a sulfonyl group, and an amino group, and may be the same or different.) The filler (C) having an average particle size of 2 μm or less is spherical silica surface-treated with a surface treatment agent having at least one of a phenyl group, an epoxy group, an aminophenyl group and a vinyl group. The positive photosensitive resin composition according to any one of claims 1 to 3. A dry film having a resin layer obtained by applying the positive photosensitive resin composition according to any one of claims 1 to 4 to a film and drying the film. A cured product obtained by curing the resin layer of the positive photosensitive resin composition according to any one of claims 1 to 4 or the dry film according to claim 5. An electronic component having the cured product according to claim 6.