JP6398364B2 - 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 patterned cured film, and an electronic component.

  With the miniaturization of semiconductor integrated circuits, an interlayer insulating film called a low-k layer for reducing the dielectric constant is required. Since the low-k layer has a pore structure, there is a problem that the mechanical strength is lowered. In order to protect such an interlayer insulating film having a low mechanical strength, a cured film formed of a polyimide resin is used. The cured film is required to have a thick film forming property and a high elastic modulus. However, as the cured film becomes thicker and has a higher elastic modulus, the stress after curing increases and the warpage of the semiconductor wafer increases, which may cause problems during transportation and wafer fixing.

  In addition, from the viewpoint of protecting the low-k layer, when the resin film is thickened, there is a problem that the transmittance of i-line used for forming a pattern on the resin film is lowered and the pattern cannot be formed. .

  In order to solve the above-mentioned problems, Patent Documents 1 and 2 propose polyimide precursors that exhibit good i-ray permeability and that provide a cured film with low stress.

JP 2000-313743 A International Publication No. 2006/008991

  However, when patterning on a substrate using a polyimide precursor described in Patent Documents 1 and 2 and a photosensitive resin composition containing an oxime ester compound, depending on the material of the base on which the photosensitive resin composition is applied, There are problems in terms of resolution, such as residues in the opening after development, a large difference between the mask dimension and the opening dimension, and the pattern itself not opening.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive resin composition capable of stably forming a pattern with good resolution regardless of the base material to which the photosensitive resin composition is applied, a method for producing a patterned cured film using the same, and an electronic component Is to provide.

  Since the present inventors have various base surfaces such as resin, SiO, SiN, Cu, Al, Ni on the base on the substrate to which the photosensitive resin composition is applied, and the degree of scattering of the active rays is different, Under the influence of scattering by the ground during the exposure, the periphery of the pattern was exposed and insolubilized by the scattered active light, and it was found out that a residue was generated or a difference between the mask size and the opening size occurred, resulting in the present invention. .

（式（２１）中、Ｒ_１１は、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数４〜１０のシクロアルキル基、フェニル基又はトリル基を示し、Ｒ_１２は、炭素数１〜１２のアルキル基、炭素数４〜１０のシクロアルキル基、フェニル基又はトリル基を示す。Ｒ_１３は、置換若しくは無置換のベンゾイル基、置換若しくは無置換のフルオレニル基又は置換若しくは無置換のカルバゾリル基を示す。）

（式（２６）中、Ｒ_１７、Ｒ_１８及びＲ_１９はそれぞれ独立に、炭素数１〜２０のアルキル基、又は置換若しくは無置換の炭素数６〜２０のアリール基を示す。）

（式（２７）中、Ｒ_２０、Ｒ_２１及びＲ_２２はそれぞれ独立に、炭素数１〜２０のアルキル基、又は置換若しくは無置換の炭素数６〜２０のアリール基を示す。）

（式（２８）中、Ｒ_２３〜Ｒ_２６はそれぞれ独立に、炭素数１〜２０のアルキル基、又は置換若しくは無置換の炭素数６〜２０のアリール基を示す。）
４．前記（Ａ）成分１００質量部に対して、前記（Ｂ１）成分を０．０１〜１．５質量部、前記（Ｂ２）成分を１〜１０質量部含む１〜３のいずれか一項に記載の感光性樹脂組成物。
５．前記（Ａ）成分が下記式（１）で表される構造単位を有するポリイミド前駆体である１〜４のいずれか一項に記載の感光性樹脂組成物。

（式（１）中、Ａは下記式（２ａ）〜（２ｄ）で表される４価の有機基のいずれかであり、Ｂは下記式（３）で表される２価の有機基である。Ｒ^１及びＲ^２は各々独立に水素原子又は１価の有機基である。Ｒ^１及びＲ^２の少なくとも一方が前記炭素−炭素不飽和二重結合を有する１価の有機基である。）

（上記式中、Ｘ及びＹは、各々独立に、各々が結合するベンゼン環と共役しない２価の基又は単結合を示す。）

（式（３）中、Ｒ^３〜Ｒ^１０は、各々独立に水素原子、フッ素原子又は１価の有機基を表し、Ｒ^３〜Ｒ^１０の少なくとも１つはフッ素原子又はトリフルオロメチル基を表す。）
６．前記ポリイミド前駆体が、さらに下記式（１９）で表される構造単位を有する５に記載の感光性樹脂組成物。

（式（１９）中、Ｄは下記式（２０）で表される４価の有機基である、Ｂは上記式（３）で表される２価の有機基である。Ｒ^１及びＲ^２は各々独立に水素原子又は１価の有機基である。）

（式中、Ｚは酸素原子又は硫黄原子を示す。）
７．１〜６のいずれか一項に記載の感光性樹脂組成物を基板上に塗布及び乾燥して塗膜を形成する工程と、
前記塗膜に活性光線を照射してパターン状に露光する工程と、
未露光部を現像によって除去してパターン樹脂膜を得る工程と、
前記パターン樹脂膜を加熱処理する工程とを含有するパターン硬化膜の製造方法。
８．７に記載の製造方法により得られるパターン硬化膜を、層間絶縁膜層及び表面保護膜層の少なくとも一方として有する電子部品。 According to the present invention, the following photosensitive resin composition and the like are provided.
1. The photosensitive resin composition containing the following (A) component, (B1) component, and (B2) component.
(A) component: at least one polymer of polyimide and polyimide precursor having a monovalent organic group having a carbon-carbon unsaturated double bond (B1) component: a compound that generates radicals by actinic radiation. A compound satisfying the following conditions (i) and (ii):
(I) A composition containing 2 parts by mass alone and 100 parts by mass of the component (A) is coated on a substrate, dried, exposed at an exposure amount of 250 mJ / cm ² and developed, and the remaining film rate. Is a composition containing 2 parts by mass of (ii) alone and 100 parts by mass of the component (A), dried on a substrate, exposed at an exposure amount of 50 mJ / cm ² and developed. (B2) component: a compound that generates radicals by actinic radiation and satisfies the following conditions (iii) and (iv):
(Iii) a singly 2 parts by weight, the (A) applying a composition comprising a 100 parts by weight of the component on the substrate, ^dried, either 300mJ / cm 2, 350mJ / cm 2 and 400 mJ / cm ² The remaining film ratio after exposure and development with an exposure amount of 80% or more and less than 90%,
(Iv) A composition containing 2 parts by mass alone and 100 parts by mass of the component (A) is applied on a substrate and dried to be 30 mJ / cm ² , 60 mJ / cm ² , 80 mJ / cm ² and 90 mJ /. 1. The residual film ratio after exposure and development at any exposure dose of cm ² is 20% or less. The photosensitive resin composition containing the following (A) component, (B1) component, and (B2) component.
(A) component: at least one polymer of a polyimide and a polyimide precursor having a monovalent organic group having a carbon-carbon unsaturated double bond,
(B1) component: O-acyl oxime compound,
(B2) component: acylphosphine oxide compound or acyl dialkoxymethane compound3. The component (B1) is a compound represented by the following formula (21), and the component (B2) is selected from the group consisting of compounds represented by the following formulas (26), (27) and (28) The photosensitive resin composition of 1 or 2 which is the above compound.

(In the formula (21), R ₁₁ represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group, and R ₁₂ represents Represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group, and R ₁₃ represents a substituted or unsubstituted benzoyl group, a substituted or unsubstituted fluorenyl group, a substituted or Represents an unsubstituted carbazolyl group.)

(In the formula (26), R ₁₇ , R ₁₈ and R ₁₉ each independently represents an alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.)

(In formula (27), R ₂₀ , R ₂₁ and R ₂₂ each independently represents an alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.)

(In formula (28), R _{23 to} R ₂₆ each independently represents an alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.)
4). The component (B1) is 0.01 to 1.5 parts by mass, and the component (B2) is 1 to 10 parts by mass with respect to 100 parts by mass of the component (A). Photosensitive resin composition.
5. The photosensitive resin composition as described in any one of 1-4 whose said (A) component is a polyimide precursor which has a structural unit represented by following formula (1).

(In the formula (1), A is any one of tetravalent organic groups represented by the following formulas (2a) to (2d), and B is a divalent organic group represented by the following formula (3). R ¹ and R ² are each independently a hydrogen atom or a monovalent organic group, and at least one of R ¹ and R ² is a monovalent organic group having the carbon-carbon unsaturated double bond. )

(In the above formula, X and Y each independently represent a divalent group or a single bond that is not conjugated to the benzene ring to which each is bonded.)

(In formula (3), R ^{3 to} R ¹⁰ each independently represent a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ^{3 to} R ¹⁰ represents a fluorine atom or a trifluoromethyl group. .)
6). 6. The photosensitive resin composition according to 5, wherein the polyimide precursor further has a structural unit represented by the following formula (19).

(In formula (19), D is a tetravalent organic group represented by the following formula (20), B is a divalent organic group represented by the above formula (3). R ¹ and R ² Are each independently a hydrogen atom or a monovalent organic group.)

(In the formula, Z represents an oxygen atom or a sulfur atom.)
The process of apply | coating and drying the photosensitive resin composition as described in any one of 7.1-6 on a board | substrate, and forming a coating film,
Irradiating the coating film with an actinic ray to expose it in a pattern; and
Removing unexposed portions by development to obtain a patterned resin film;
A process for producing a cured pattern film, comprising a step of heat-treating the patterned resin film.
An electronic component having a patterned cured film obtained by the production method according to 8.7 as at least one of an interlayer insulating film layer and a surface protective film layer.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which can form a pattern with a sufficient resolution stably regardless of the base material which apply | coats the photosensitive resin composition, the manufacturing method of a pattern cured film using the same, and an electronic component Can be provided.

  Hereinafter, a photosensitive resin composition of the present invention, a method for producing a patterned cured film using the same, and an embodiment of an electronic component will be described in detail. The present invention is not limited to the following embodiments.

In this specification, “(meth) acrylate” means “acrylate” or “methacrylate” corresponding thereto. Similarly, “(meth) acrylic acid” means “acrylic acid” or “methacrylic acid”, “(meth) acrylic group” means “acrylic group” or “methacrylic group”, and “( “Meth) acryloyl” means “acryloyl” or “methacryloyl”.
Further, “A or B” only needs to include either “A” or “B”, and may be “A + B”.

[Photosensitive resin composition]
The 1st aspect of the photosensitive resin composition of this invention is a photosensitive resin composition containing the following (A) component, (B1) component, and (B2) component.
(A) component: at least one polymer of polyimide and polyimide precursor having a monovalent organic group having a carbon-carbon unsaturated double bond (B1) component: a compound that generates radicals by actinic radiation. A composition containing 2 parts by mass of the compound (i) alone satisfying the following conditions (i) and (ii) and 100 parts by mass of the component (A) is coated on a substrate and dried, and the exposure amount is 250 mJ / cm. exposed with ^2, and the residual film rate after development more than 90% (ii) alone 2 parts by weight, coating said composition containing a component (a) 100 parts by weight on the substrate, dried, exposed (B2) Component: A compound that generates radicals by actinic ray radiation and satisfies the following conditions (iii) and (iv) (the amount of residual film after exposure and development at an amount of 50 mJ / cm ² is 80% or more. iii) 2 parts by mass alone, A composition containing 100 parts by mass of component (A) is applied onto a substrate, dried, exposed at an exposure dose of 300 mJ / cm ² , 350 mJ / cm ² and 400 mJ / cm ² and developed. (Iv) A composition containing 2 parts by mass alone and 100 parts by mass of the component (A) is applied onto a substrate and dried to yield 30 mJ / cm ² , 60 mJ. / Cm ² , 80 mJ / cm ^2, and 90 mJ / cm ² of exposure amount, and the remaining film ratio after development is 20% or less

(A) when the component and the component (B1) alone and the prepared composition, exposure and exposure at 250 mJ / cm ^2, the residual film rate after development is 90% or more, the exposure amount 50 mJ / cm ² The residual film ratio after exposure and development is 80% or more.
(A) when the component and the component (B2) alone and compositions were ^prepared, exposed with either exposure of 300mJ / cm 2, 350mJ / cm 2 and 400 mJ / cm ^2, remaining after development next film ratio ^{80% ~90%, 30mJ / cm} 2, 60mJ / cm 2, were exposed in one of the exposure amount of 80 mJ / cm ² and 90 mJ / cm ^2, the residual film rate after development is 20% or less It becomes.
In the case of a photosensitive resin composition containing the component (A) and such a component (B1) and component (B2), the opening of the pattern resin film after development on the substrate on which materials having different reflectances are mixed is used. There is no residue and a pattern can be formed with good resolution.

The mechanism of expression of the effect by having the above configuration can be inferred as follows.
That is, the component (B1) has very high sensitivity because the coating film has a high residual film rate when exposed and developed at exposure amounts of 250 mJ / cm ² and 50 mJ / cm ² . For this reason, since the overexposure is performed at the recommended exposure amount, it is very easily affected by the reflected light from the substrate surface, which causes generation of residue in the opening. On the other hand, (B2) ^component, since the 300mJ / cm 2, 350mJ / cm 2 and 400 mJ / exposure in one of the exposure amount of cm ^2, coating the film retention upon development is 80-90% Susceptible to oxygen inhibition and poor surface curability. However, when exposed and developed at an exposure amount of 30 mJ / cm ² , 60 mJ / cm ² , 80 mJ / cm ^2, and 90 mJ / cm ² , the residual film ratio of the coating film is low and the contrast is very high. It has an appropriate threshold that does not decompose with a small amount of scattered light. Therefore, when the photosensitive resin composition contains the component (A), the component (B1) and the component (B2), the surface curability is good without being affected by oxygen inhibition, and the scattered light from the base is not affected. Since it is not affected, a pattern with a good shape having a high residual film ratio after development, no development residue, and an opening dimension faithful to the mask dimension can be formed.

In addition, in (B1) component and (B2) component, the recommended exposure amount is 200-400 mJ / cm < ² >. The recommended exposure amount is usually an exposure amount at which the remaining film ratio is 85% or more in the photosensitive material, there is no fine line peeling due to insufficient crosslinking density, and the resolution is the best.

Hereinafter, each component will be described.
(A) component A conventionally well-known thing can be especially used for the polyimide precursor which has a monovalent organic group which has a carbon-carbon unsaturated double bond without a restriction | limiting.
Among these, it is preferable to have a structure represented by Formula (1).

式（１）中、Ａは下記式（２ａ）〜（２ｄ）で表される４価の有機基のいずれかであり、Ｂは下記式（３）で表される２価の有機基である。Ｒ^１及びＲ^２は各々独立に水素原子又は１価の有機基である。Ｒ^１及びＲ^２の少なくとも一方は炭素−炭素不飽和二重結合を有する１価の有機基である。

In formula (1), A is any of the tetravalent organic groups represented by the following formulas (2a) to (2d), and B is a divalent organic group represented by the following formula (3). . R ¹ and R ² are each independently a hydrogen atom or a monovalent organic group. At least one of R ¹ and R ² is a monovalent organic group having a carbon-carbon unsaturated double bond.

上記式中、Ｘ及びＹは、各々独立に、各々が結合するベンゼン環と共役しない２価の基又は単結合を示す。

In the above formula, X and Y each independently represent a divalent group or a single bond that is not conjugated to the benzene ring to which each is bonded.

式（３）中、Ｒ^３〜Ｒ^１０は、各々独立に水素原子、フッ素原子又は１価の有機基を表し、Ｒ^３〜Ｒ^１０の少なくとも１つはフッ素原子、メチル基又はトリフルオロメチル基を表す。

In formula (3), R ^{3 to} R ¹⁰ each independently represent a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ^{3 to} R ¹⁰ is a fluorine atom, a methyl group or a trifluoromethyl group. Represents.

A in the formula (1) is a structure derived from tetracarboxylic dianhydride used as a raw material, and is any of the tetravalent organic groups represented by the above formulas (2a) to (2d).
In X and Y, examples of the divalent group that is not conjugated to the benzene ring include an oxygen atom, a dimethylmethylene group, a bis (trifluoromethyl) methylene group, a dimethylsilylene group, and a methyltrifluoromethylmethylene group.

  Examples of tetracarboxylic dianhydrides that give the structure of A include pyromellitic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 4,4′-biphenyltetracarboxylic dianhydride, The tetracarboxylic dianhydride represented by Formula (4)-Formula (10) is mentioned. These may be used alone or in combination of two or more tetracarboxylic dianhydrides.

B in Formula (1) is a structure derived from diamine used as a raw material, and is a divalent organic group represented by Formula (3).
Examples of the monovalent organic group represented by R ^{3 to} R ¹⁰ include a methyl group and a trifluoromethyl group.

As the diamine that gives the structure of B, it is preferable that at least one of R ^{3 to} R ¹⁰ is a fluorine atom, a methyl group, or a trifluoromethyl group, from the viewpoint of good i-line transmittance and low stress. Is preferably a fluorine atom, a methyl group or a trifluoromethyl group, more preferably two or more are a methyl group or a trifluoromethyl group.
Among these, diamines represented by the following formulas (11) to (18) are preferably used. These may be used alone or in combination of two or more diamines.

The monovalent organic group having a carbon-carbon unsaturated double bond is preferably an ethylenically unsaturated group, more preferably a (meth) acryloxyalkyl group having 1 to 10 carbon atoms, and a (meth) acryloxyethyl group. (Meth) acryloxypropyl group or (meth) acryloxybutyl group is more preferable.
When the component (A) has a monovalent organic group having a carbon-carbon unsaturated double bond, crosslinking between molecular chains by radical polymerization is possible in combination with a compound that generates radicals upon irradiation with actinic rays. .

R ¹ and R ^{2 in} Formula (1) are at least one monovalent organic group having a carbon-carbon unsaturated double bond, and the other is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or It may be a cycloalkyl group.

（式（１９）中、Ｄは下記式（２０）で表される４価の有機基である、Ｂは上記式（３）で表される２価の有機基である。Ｒ^１及びＲ^２は各々独立に水素原子又は１価の有機基である。）

（式中、Ｚは酸素原子又は硫黄原子を示す。） The above polyimide precursor may further have a structural unit represented by the following formula (19) for the purpose of improving i-line transmittance, adhesion after curing, and mechanical properties.

(In formula (19), D is a tetravalent organic group represented by the following formula (20), B is a divalent organic group represented by the above formula (3). R ¹ and R ² Are each independently a hydrogen atom or a monovalent organic group.)

(In the formula, Z represents an oxygen atom or a sulfur atom.)

B in the formula (19) is the same as B in the formula (1), ^{R 1} and ^{R 2} in the formula (19) is the same as ^{R 1} and ^{R 2} of formula (1).
At least one of R ¹ and R ² is preferably a monovalent organic group having the above-described carbon-carbon unsaturated double bond. Z is preferably an oxygen atom.

  D in the formula (19) is a structure derived from a tetracarboxylic dianhydride as a raw material, and shows a structure of a tetravalent organic group represented by the formula (20). Examples of the tetracarboxylic dianhydride that gives the structure of D include 4,4'-oxydiphthalic dianhydride and 4,4'-thiodiphthalic dianhydride. These may be used alone or in combination of two or more.

  In the polyimide precursor which has a structural unit represented by Formula (1) and a structural unit represented by Formula (19), it is represented by Formula (1) from the viewpoint of achieving both low stress and good i-line transmittance. The molar ratio of the structural unit represented by Formula (19) is preferably 5/5 to 9/1, more preferably 6/4 to 9/1, and 7/3 to 3/3. More preferably, it is 9/1.

  There is no restriction | limiting in particular in the synthesis | combining method of the said polyimide precursor, It can synthesize | combine by a conventionally well-known method. For example, it can be synthesized by addition polymerization of tetracarboxylic dianhydride and diamine. Alternatively, the tetracarboxylic dianhydride as a raw material can be synthesized into a diester derivative, converted to an acid chloride, and condensed in the presence of a diamine and a basic compound (for example, pyridine).

  Examples of the polyimide include polyimide formed from the above polyimide precursor.

As for the molecular weight of the polymer of component (A), the weight average molecular weight in terms of polystyrene is preferably 10,000 to 100,000, more preferably 15,000 to 100,000, and still more preferably 20,000 to 85,000. If the weight average molecular weight is less than 10,000, the stress after curing may not be sufficiently reduced. If the weight average molecular weight is more than 100,000, the solubility in a solvent may be reduced, or the viscosity of the solution may be increased and the handleability may be reduced. There is.
The weight average molecular weight can be measured by a gel permeation chromatography method and is determined by conversion using a standard polystyrene calibration curve.

Component (B) The component (B) is a compound (photosensitive agent) that generates radicals when irradiated with actinic rays.

(B1) component When the component (B1) is prepared as a composition alone with the component (A) (that is, not including the component (B2)), it is exposed and developed at an exposure amount of 250 mJ / cm ² . It is a compound in which the remaining film ratio of the subsequent coating film is 90% or more. At this time, the remaining film ratio is preferably 92% or more, more preferably 93% or more, further preferably 94% or more, and particularly preferably 95% or more.
The residual film ratio after development may be 90% or more at any exposure amount of 100, 150, 200, 300, 350, and 400 mJ / cm ² .

Moreover, (B1) component is a compound which becomes 80% or more of the residual film rate of the coating film after exposing and developing with the exposure amount of 50 mJ / cm < ² >. In this case, the remaining film ratio is preferably 81% or more, more preferably 82% or more, further preferably 84% or more, and particularly preferably 85% or more.
The remaining film ratio after development may be 80% or more with an exposure amount of 20, or 30 mJ / cm ² .

  Said composition may contain the below-mentioned (C) component, (D) component, and (E) component with the below-mentioned content.

When the above composition is applied, dried, and formed into a film, the film thickness is preferably 3 to 20 μm, more preferably 5 to 15 μm. The heat drying during film formation is preferably from 80 to 160 ° C, more preferably from 100 to 160 ° C. The heat drying time is preferably 60 to 300 seconds, more preferably 90 to 210 seconds.
In the said composition, 2 mass parts of (B1) components are contained with respect to 100 mass parts of (A) component. (A) You may contain in 0.01-5 mass parts or 1-3 mass parts of (B1) component with respect to 100 mass parts of components.
The exposure is preferably performed with i-line.
The developer is preferably cyclopentanone. The development temperature is preferably 20 to 25 ° C. The development time is preferably set to 1.5 to 2.5 times as long as the time required for the unexposed portion to be completely dissolved after being immersed in the developer.

  The remaining film ratio is obtained by dividing the film thickness after development by the film thickness after coating and drying and multiplying by 100.

式（２１）中、Ｒ_１１は、炭素数１〜１２のアルキル基、炭素数１〜１２のアルコキシ基、炭素数４〜１０のシクロアルキル基、フェニル基又はトリル基を示し、Ｒ_１２は、炭素数１〜１２のアルキル基、炭素数４〜１０のシクロアルキル基、フェニル基又はトリル基を示す。
Ｒ_１１及びＲ_１２は、炭素数１〜８のアルキル基、炭素数４〜６のシクロアルキル基、フェニル基又はトリル基であることが好ましく、炭素数１〜４のアルキル基、炭素数４〜６のシクロアルキル基、フェニル基又はトリル基であることがより好ましく、メチル基、シクロペンチル基、フェニル基又はトリル基であることがさらに好ましい。
Ｒ_１３は、置換若しくは無置換のベンゾイル基、置換若しくは無置換のフルオレニル基又は置換若しくは無置換のカルバゾリル基であり、後述の式（２２）〜（２５）に示す化合物が有するＲ_１３に対応する基であることが好ましい。 The component (B1) is preferably a compound represented by the following formula (21), which is an O-acyloxime compound.

In Formula (21), R ₁₁ represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group, and R ₁₂ represents An alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group is shown.
R ₁₁ and R ₁₂ are preferably an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 6 carbon atoms, a phenyl group, or a tolyl group, and an alkyl group having 1 to 4 carbon atoms, or 4 to 4 carbon atoms. 6 is more preferably a cycloalkyl group, a phenyl group or a tolyl group, and further preferably a methyl group, a cyclopentyl group, a phenyl group or a tolyl group.
R ₁₃ is a substituted or unsubstituted benzoyl group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted carbazolyl group, and corresponds to R ₁₃ included in the compounds represented by the following formulas (22) to (25). It is preferably a group.

式（２２）中、Ｒ_１１及びＲ_１２は上記と同様である。
Ｒ_１４は、−Ｈ、−ＯＨ、−ＣＯＯＨ、−Ｏ（ＣＨ_２）ＯＨ、−Ｏ（ＣＨ_２）_２ＯＨ、−ＣＯＯ（ＣＨ_２）ＯＨ、又は−ＣＯＯ（ＣＨ_２）_２ＯＨを示し、−Ｈ、−Ｏ（ＣＨ_２）ＯＨ、−Ｏ（ＣＨ_２）_２ＯＨ、−ＣＯＯ（ＣＨ_２）ＯＨ、又は−ＣＯＯ（ＣＨ_２）_２ＯＨであることが好ましく、−Ｈ、−Ｏ（ＣＨ_２）_２ＯＨ、又は−ＣＯＯ（ＣＨ_２）_２ＯＨであることがより好ましい。 The component (B1) is preferably any one of compounds represented by the following formulas (22) and (23) from the viewpoint of improving photocurability.

In formula (22), R ₁₁ and R ₁₂ are the same as described above.
R ₁₄ represents —H, —OH, —COOH, —O (CH ₂ ) OH, —O (CH ₂ ) ₂ OH, —COO (CH ₂ ) OH, or —COO (CH ₂ ) ₂ OH, _{-H, -O (CH 2) OH} , -O (CH 2) 2 OH, -COO (CH 2) OH, or -COO _{(CH 2)} is preferably from 2 OH, -H, -O (CH ₂ ) ₂ OH or —COO (CH ₂ ) ₂ OH is more preferable.

式（２３）中、Ｒ_１１及びＲ_１２は上記と同様である。Ｒ_１５は、炭素数１〜６のアルキル基を示し、エチル基であることが好ましい。
Ｒ_１６は、炭素数１〜１２のアルキル基、又はアセタール結合を有する有機基であり、メチル基又は後述する式（２３−２）に示す化合物が有するＲ_１６に対応する置換基であることが好ましい。ｄは１〜３の整数であり、1又は２の整数であることが好ましい。

In formula (23), R ₁₁ and R ₁₂ are the same as described above. R ₁₅ represents an alkyl group having 1 to 6 carbon atoms, and is preferably an ethyl group.
R ₁₆ is an alkyl group having 1 to 12 carbon atoms or an organic group having an acetal bond, and is a substituent corresponding to R ₁₆ included in a methyl group or a compound represented by formula (23-2) described later. preferable. d is an integer of 1 to 3, and is preferably an integer of 1 or 2.

Examples of the compound represented by the formula (22) include a compound represented by the following formula (22-1) and a compound represented by the following formula (22-2). The compound represented by the following formula (22-1) is available as IRGACURE OXE-01 (manufactured by BASF Corporation).

Examples of the compound represented by the above formula (23) include compounds represented by the following formula (23-1) or (23-2). IRGACURE OXE-02 (manufactured by BASF Corporation) and Adekaoptomer N-1919 (manufactured by ADEKA Corporation) are available.

In addition, as the component (B1), a compound represented by the following formula (24) or (29) can also be used.

Moreover, you may use the compound represented by following formula (25) as (B1) component.

As content of (B1) component, it is preferable that it is 0.01-1.5 mass part with respect to 100 mass parts of (A) component, and it is more preferable that it is 0.05-1.0 mass part. Preferably, it is 0.05-0.8 mass part, More preferably, it is 0.1-0.7 mass part, It is very preferable that it is 0.1-0.5 mass part.
When the component (B1) is within the above range, the influence of oxygen inhibition can be suppressed and the remaining film rate can be improved.

Component (B2) Component (B2) is one of 300, 350, and 400 mJ / cm ² when prepared as a composition alone with component (A) (that is, not including component (B1)). It is a compound in which the residual film ratio of the coating film after exposure and development with an exposure amount is 80% or more and less than 90%. The remaining film ratio is preferably 82% or more and 89% or less, and more preferably 84% or more and 88% or less.

Further, (B2) ^component exposed by either exposure of 30mJ / cm 2, 60mJ / cm 2, and 90 mJ / cm ^2, the residual film ratio of the coating film after developing is 20% or less. The remaining film ratio is preferably 18% or less, and more preferably 16% or less.

  Said composition may contain the below-mentioned (C) component, (D) component, and (E) component with the below-mentioned content.

  In said composition, 2 mass parts of (B2) component is contained with respect to 100 mass parts of (A) component. You may contain in 2-4 mass parts of (B2) component with respect to 100 mass parts of (A) component.

  The film thickness, heat drying, developer, and development conditions are the same as those listed for the component (B1).

  The component (B2) is preferably an acyl phosphine oxide compound or an acyl dialkoxymethane compound.

（式（５）中、Ｒ_１７、Ｒ_１８及びＲ_１９はそれぞれ独立に、炭素数１〜２０のアルキル基、又は置換若しくは無置換の炭素数６〜２０のアリール基を示す。）

（式（２７）中、Ｒ_２０、Ｒ_２１及びＲ_２２はそれぞれ独立に、炭素数１〜２０のアルキル基、又は置換若しくは無置換の炭素数６〜２０のアリール基を示す。） The acylphosphine oxide compound is preferably a compound represented by the formula (26) or (27) from the viewpoint of improving photocurability and suppressing residue in the opening.

(In Formula (5), R <_17> , R <_18> and R < ₁₉ > show a C1-C20 alkyl group or a substituted or unsubstituted C6-C20 aryl group each independently.)

(In formula (27), R ₂₀ , R ₂₁ and R ₂₂ each independently represents an alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.)

The alkyl group for R _{17 to} R ₂₂ may be any of a linear, branched, and cyclic alkyl group. Moreover, it is preferable that carbon number is 5-10. In addition, the aryl group in R _{17 to} R ₂₂ preferably has 6 to 12 carbon atoms, and more preferably a phenyl group or a naphthyl group.

  Examples of the substituent for the aryl group include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 4 carbon atoms.

Among these, it is preferable that R < ₁₇ > -R < ₂₂ > is a substituted or unsubstituted aryl group.

  Specifically, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide or bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is preferable as the acylphosphine oxide compound. These are commercially available products such as LUCIRIN TPO and IRGACURE 819 (both manufactured by BASF Corporation).

式（２８）中、Ｒ_２３〜Ｒ_２６はそれぞれ独立に、炭素数１〜２０のアルキル基、又は置換若しくは無置換の炭素数６〜２０のアリール基を示す。
Ｒ_２３〜Ｒ_２６は上記Ｒ_１７〜Ｒ_２２と同様である。 As the acyl dialkoxymethane compound, a compound represented by the formula (28) is preferable.

In formula (28), R _{23 to} R ₂₆ each independently represents an alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.
R _{23 to} R ₂₆ are the same as R _{17 to} R ₂₂ described above.

As content of (B2) component, it is preferable that it is 1-10 mass parts with respect to 100 mass parts of (A) component, It is more preferable that it is 1.5-9 mass parts, 2-8 masses More preferably, it is a part.
(B2) When a component exists in the said range, the crosslinking reaction by the reflected light from a board | substrate can be suppressed.

(C) Component The resin composition of the present invention may contain an organosilane compound as the (C) component in order to further improve the adhesion to a substrate such as a silicon substrate after curing.
Organic silane compounds include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-glycidoxypropyltrimethoxy. Silane, γ- (meth) acryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyl Triethoxysilane, triethoxysilylpropylethyl carbamate, 3- (triethoxysilyl) propyl succinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopro Examples include pyrtrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

  (C) When it contains a component, it is preferable that content of (C) component shall be 0.1-30 mass parts with respect to 100 mass parts of (A) component, and shall be 1-20 mass parts. Is more preferably 3 to 10 parts by mass.

(D) component The photosensitive resin composition of this invention may contain a solvent as (D) component.
The solvent is preferably a polar solvent that completely dissolves the component (A) such as a polyimide precursor, such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethyl. Urea, hexamethylphosphoric triamide, γ-butyrolactone, δ-valerolactone, γ-valerolactone, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, propylene carbonate, ethyl lactate, 1,3-dimethyl-2-imidazolide Non etc. are mentioned. These may be used alone or in combination of two or more. Among these, N-methyl-2-pyrrolidone is preferably used from the viewpoint of room temperature viscosity stability.

  The content of the component (D) is preferably 100 to 280 parts by mass, more preferably 110 to 260 parts by mass, and 130 to 170 parts by mass with respect to 100 parts by mass of the component (A). More preferably.

(E) component The photosensitive resin composition of this invention may also contain the photopolymerizable compound which has an ethylenically unsaturated bond as (E) component.
As photopolymerizable compounds, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, 1,3- (meth) acryloyloxy-2-hydroxypropane, methylenebisacrylamide, N N- dimethylacrylamide, N- methylol acrylamide. These may be used alone or in combination of two or more.

  (E) When it contains a component, it is preferable that the content shall be 1-100 mass parts with respect to 100 mass parts of (A) component, 3-75 mass parts is more preferable, 5-50 mass parts Is more preferable. If the content is 1 part by mass or more, better photosensitive characteristics can be imparted, and if it is 100 parts by mass or less, the heat resistance of the cured film can be further improved.

In addition, the resin composition of the present invention may contain a radical polymerization inhibitor or a radical polymerization inhibitor in order to ensure good storage stability.
Examples of radical polymerization inhibitors or radical polymerization inhibitors include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, Examples thereof include N-phenyl-2-naphthylamine, cuperone, 2,5-toluquinone, tannic acid, parabenzylaminophenol, and nitrosamines. These may be used alone or in combination of two or more.

  When the radical polymerization inhibitor or the radical polymerization inhibitor is contained, the content thereof is preferably 0.01 to 30 parts by mass, and 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (A). More preferably, it is 0.05-5 mass parts. If the content is less than 0.01 parts by mass, the storage stability tends to decrease, and if it is more than 30 parts by mass, the heat resistance of the cured film formed from the photosensitive resin composition of the present invention may decrease. .

  Moreover, the photosensitive resin composition of the present invention may contain a rust preventive agent in order to ensure stability and adhesion to the Cu substrate. Examples of the rust preventive include benzotriazole, carboxybenzotriazole, and tetrazole. These may be used alone or in combination of two or more.

  In the photosensitive resin composition of the present invention, the components (A) to (E), the radical polymerization inhibitor, the radical polymerization inhibitor and the rust inhibitor are 95% by mass or more, 98% by mass or 100% by mass. Good.

[Method for producing patterned cured film]
The method for producing a patterned cured film of the present invention includes a step of applying and drying the above-described photosensitive resin composition on a substrate to form a coating film, and a step of exposing the coating film to a pattern by irradiating the coating with actinic rays. And a step of removing the unexposed portion by development to obtain a pattern resin film, and a step of heat-treating the pattern resin film.
Hereinafter, each step will be described.

Application can be performed by dipping, spraying, screen printing, spin coating, or the like.
Examples of the substrate include a silicon wafer, a metal substrate, and a ceramic substrate.
The solvent is removed by heating by drying. Examples of the apparatus include a hot plate and an oven. The heating temperature for removing the solvent by heating is preferably 80 to 150 ° C., and the heating time is preferably 60 seconds to 300 seconds. By removing the solvent by heating, a non-adhesive coating film can be formed.

As the active light to be irradiated, ultraviolet rays such as i rays, far ultraviolet rays, visible rays, electron beams, X-rays and the like can be used. i-line is most preferred.
The pattern exposure is not particularly limited, but is preferably performed through a mask on which a desired pattern is drawn.

  The developer is not particularly limited, but flame retardant solvents such as 1,1,1-trichloroethane, alkali aqueous solutions such as aqueous sodium carbonate and tetramethylammonium hydroxide, N, N-dimethylformamide, dimethyl sulfoxide, Good solvents such as N, N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, γ-butyrolactone, acetates, etc., and these good solvents and poor solvents such as lower alcohols, water, and aromatic hydrocarbons A mixed solvent or the like is used.

The development temperature is preferably 20 to 25 ° C. Usually, it is 23 degreeC, for example. The development time is preferably set as 1.5 to 2.5 times the time until the coating film formed from the photosensitive resin composition of the present invention is immersed in the developer and completely dissolved. . It is more preferable to set 2 times as the development time.
After development, rinsing with a poor solvent or the like may be performed as necessary.
By developing and removing the unexposed portions by development, a desired pattern resin film can be obtained.

The conditions for the heat treatment of the pattern resin film are, for example, 80 to 400 ° C. and 5 to 300 minutes. Thereby, imidization can be advanced and the pattern cured film containing a polyimide can be obtained.
When the polyimide is used after curing, the chemical resistance and heat resistance of the pattern cured film can be improved.

  The patterned cured film produced by the method of the present invention can be used as an interlayer insulating film layer, a surface protective film layer or the like of an electronic component.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, this invention is not limited to these Examples.

[(A) component]
Synthesis Example 1 (Synthesis of Polymer A1)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 195.564 g of pyromellitic acid-hydroxyethyl methacrylate diester (PMDA (HEMA)) solution and 4,4′-oxydiphthalic acid-hydroxyethyl methacrylate diester (ODPA ( HEMA)) solution (58.652 g) was added, and then 25.9 g (217.8 mmol) of thionyl chloride was added dropwise using an addition funnel so as to keep the reaction solution temperature at 10 ° C. or lower. After the addition of thionyl chloride was completed, the reaction was carried out for 2 hours under ice cooling to obtain a solution of PMDA (HEMA) and ODPA (HEMA) acid chloride. Then, using a dropping funnel, 31.696 g (99.0 mmol) of 2,2′-bis (trifluoromethyl) benzidine, 34.457 g (435.6 mmol) of pyridine, 0.076 g (0.693 mmol) of hydroquinone -90.211 g of methylpyrrolidone solution was added dropwise while cooling with ice so that the temperature of the reaction solution did not exceed 10 ° C. The reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamic acid ester. The weight average molecular weight determined by standard polystyrene conversion was 34,000. This was polymer A1 (pyromellitic acid-hydroxyethyl methacrylate diester / 4,4′-oxydiphthalic acid-hydroxyethyl methacrylate diester / 2,2′-bis (trifluoromethyl) benzidine condensation polymer (PMDA / ODPA / TFMB)). And
The measurement conditions of the weight average molecular weight calculated | required by GPC method standard polystyrene conversion of polymer A1 are as follows, Solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1/1 (volume ratio) with respect to 0.5 mg of polymers. )] Measured using 1 mL of solution.

Measuring device: Detector L4000UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
C-R4A Chromatopac made by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 × 2 eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / L), H ₃ PO ₄ (0.06 mol / L)
Flow rate: 1.0 mL / min, detector: UV 270 nm

Synthesis Example 2 (Synthesis of polymer A2)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 169.275 g of 3,3′-4,4′-biphenyltetracarboxylic acid-hydroxyethyl methacrylate diester (s-BPDA (HEMA)) solution and ODPA (HEMA) ) 72.777 g of the solution was added, and then 25.9 g (217.8 mmol) of thionyl chloride was added dropwise using an addition funnel while maintaining the reaction solution temperature at 10 ° C. or lower under ice cooling. After completion of the dropwise addition of thionyl chloride, the mixture was stirred for 1 hour under ice cooling to obtain a chloride solution of s-BPDA (HEMA) and ODPA (HEMA). Then, using a dropping funnel, an N-methylpyrrolidone solution 59 of 21.017 g (99.0 mmol) of 2,2′-dimethylbenzidine, 34.457 g (435.6 mmol) of pyridine, and 0.076 g (0.693 mmol) of hydroquinone. .817 g was added dropwise while cooling with ice so that the temperature of the reaction solution did not exceed 10 ° C. The reaction solution was dropped into distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain a polyamic acid ester. Similar to Synthesis Example 1, the weight average molecular weight determined by standard polystyrene conversion was 35,000. The polymer A2 (3,3′-4,4′-biphenyltetracarboxylic acid-hydroxyethyl methacrylate diester / 4,4′-oxydiphthalic acid-hydroxyethyl methacrylate diester / 2,2′-dimethylbenzidine condensation polymer (BPDA / ODPA / DMB)).

[Component (B)]
1. The following were prepared as the component (B1).
B1-1: 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) (IRGACURE-OXE-01, manufactured by BASF Corporation)
B1-2: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (IRGACURE-OXE-02, BASF Corporation) Made)
B1-3: Compound represented by the above formula (22-2) B1-4: 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime (Quantacure PDO, manufactured by IBIS Corporation)
B1-5: Compound represented by the above formula (29) (DFI-020, manufactured by Daito Chemix Co., Ltd.)
B1-6: Compound represented by the above formula (25) (Adeka Cruz NCI-831, manufactured by ADEKA Corporation)
B1-7: Compound represented by the above formula (23-2) (Adekaoptomer N-1919, manufactured by ADEKA Corporation)

2. The following were prepared as the component (B2).
B2-1: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE 819, manufactured by BASF Corporation)
B2-2: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (LUCIRIN TPO, manufactured by BASF Corporation)
B2-3: 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE-I-651, manufactured by BASF Corporation)

3. (B) Component characteristic measurement 100 parts by mass of polymer A1 obtained in Synthesis Example 1, 20 parts by mass of tetraethylene glycol dimethacrylate (TEGDMA), (B1) component, and (B2) component shown in Table 1 After dissolving in N-methyl-2-pyrrolidone (NMP), the composition of Experimental Examples 1 to 10 was obtained by pressure filtration using a 3 μm filter.

(Measurement of remaining film rate)
The obtained composition was applied onto a 6-inch silicon wafer and dried on a hot plate at 130 ° C. for 2 minutes to form a coating film having a thickness of 10 μm. The development time was set to twice the time required for this coating film to be completely dissolved by being immersed in cyclopentanone. Using a proximity exposure machine UX-1000SM (manufactured by Ushio Electric Co., Ltd.), 1000 mJ / cm ² exposure is applied to the coating film obtained by the same method through a 21-step photomask (manufactured by Hitachi Chemical Co., Ltd.). went. The exposed wafer was dipped in cyclopentanone at 23 ° C. for the above development time, followed by dip development, and then rinsed with propylene glycol monomethyl ether acetate. Next, using a contact-type film thickness meter Alpha step D-120 (XP-200) (manufactured by KLA Corporation), the film thickness of the portion where the film remained was measured, and the remaining film ratio was calculated.
Residual film ratio = (film thickness after development / film thickness after coating and drying) × 100

  Next, the relationship between the exposure amount and the remaining film rate was plotted, and the remaining film rate at the recommended exposure amount shown below and the remaining film rate at an exposure amount of 20 to 35% of the recommended exposure amount were evaluated. The results are shown in Table 1.

(1) Residual film rate at recommended exposure amount The residual film rate at the recommended exposure amount (any of ²⁰⁰ , 250, 300, 350, and 400 mJ / cm ² ) was determined.

(2) Residual film rate at 20 to 35% of the recommended exposure amount The post-development residual film rate at any exposure amount of 20 to 35% of the recommended exposure amount was determined.

Examples 1-12 and Comparative Examples 1-2
(Preparation of photosensitive resin composition)
The photosensitive resin composition of Examples 1-12 and Comparative Examples 1-2 was prepared like the Experimental Examples 1-10 by the mass part shown in Table 3.

(Residual film rate and contrast evaluation)
Similar to Experimental Examples 1 to 10, the remaining film ratio and contrast of the photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 2 were measured. The following criteria were used for the remaining film ratio and contrast. The results are shown in Table 3.
(1) Residual film ratio at recommended exposure (any of 200 to 400 mJ / cm ² ): Residual film ratio after development is 90% or more ○: Residual film ratio after development is 80% or more and less than 90% × : Residual film ratio after development is less than 80%

(2) Remaining film rate at 20 to 35% of recommended exposure amount ○: Residual film rate after development at 20 to 35% of recommended exposure amount Δ: Recommended exposure The remaining film ratio after development is more than 20% at an exposure amount of 20 to 35% of the amount, and the remaining film ratio after development is less than 80% at an exposure amount of 20% of the recommended exposure amount. 80% or more of the remaining film after development with a% exposure

(3) Contrast ○: In the evaluations (1) and (2) above, both ○ or ◎
Δ: In the evaluation of (2) above, one is ○ or ◎ and the other is Δ
×: In the evaluation of (1) or (2) above, either one is ×

(Resolution evaluation on silicon wafers with Si and Cu plating)
1. Measurement of scattered light Spectral colorimeter CM-5 (manufactured by Konica Minolta Co., Ltd.) for the scattered light intensity at 365 nm of a 6 inch silicon wafer (manufactured by E & M Co., Ltd.) and a silicon wafer with 6 inch Cu plating (manufactured by AMT Co., Ltd.) It measured using. The results are shown in Table 2.

From the above results, the silicon wafer had no scattered light, and the reflected light was only regular reflection. For this reason, it is considered that pattern skirting hardly occurs.
On the other hand, the scattered light was strong in the silicon wafer with Cu plating. For this reason, there is a possibility that pattern skirting is likely to occur.

2. Minimum opening size The photosensitive resin composition described above was applied by spin coating on a 6-inch silicon wafer or a 6-inch Cu-plated silicon wafer whose scattered light intensity was measured, and dried on a hot plate at 100 ° C. for 2 minutes. Thus, a coating film having a thickness of 10 μm was formed. The coating film through a photomask, using an i-line stepper FPA-3000iW (manufactured by Canon Inc.), and irradiated with i-rays of 50 to 500 mJ / cm ² in a predetermined pattern at 50 mJ / cm ² increments, Exposure was performed. In addition, after setting an unexposed coating film of the same thickness in cyclopentanone to be completely dissolved by dissolving it twice as a development time, and after paddle development of the exposed wafer using cyclopentanone Then, rinsing with propylene glycol monomethyl ether acetate was performed. The minimum opening dimension of the line and space pattern at this time was evaluated according to the following criteria. The results are shown in Table 3.
○: Minimum opening dimension is 8 μm or less Δ: Minimum opening dimension is more than 8 μm and 20 μm or less ×: Minimum opening dimension is more than 20 μm

3. Mask Dimension Ratio A cross section of an 8 μm isolated pattern was observed using an SEM at the exposure amount at which the minimum opening dimension was obtained, and the opening dimension on the bottom surface was evaluated according to the following criteria. The results are shown in Table 3.
A: Opening size is 6 or more and 8 μm or less ○: Opening size 3 or more and less than 6 μm

  The photosensitive resin composition of this invention can be used as materials, such as a surface protective film of an electronic component, an interlayer insulation film.

Claims (8)

Contains the following (A) component, (B1) component and (B2) component ,
The photosensitive resin composition which contains 0.01-1.5 mass part of said (B1) component, and 1-10 mass parts of said (B2) component with respect to 100 mass parts of said (A) component .
(A) component: at least one polymer of polyimide and polyimide precursor having a monovalent organic group having a carbon-carbon unsaturated double bond (B1) component: a compound that generates radicals by actinic radiation. A compound satisfying the following conditions (i) and (ii):
(I) except for solvent coating, and 20 parts by weight of tetraethylene glycol dimethacrylate, (B1) and 2 parts by mass of component alone, and the component (A) 100 parts by weight of a composition comprising only a substrate The film is dried at 130 ° C. for 2 minutes to form a coating film 1 having a thickness of 10 μm, and the development time is twice as long as it is completely dissolved by being immersed in cyclopentanone at 23 ° C.
Similarly to form a coating film 1, an i-line exposure with an exposure amount 250 mJ / cm ^2, the residual film rate after development of the developing time at 23 ° C. in cyclopentanone 90% or more of (ii) solvent except for the 20 parts by weight of tetraethylene glycol dimethacrylate, (B1) and singly 2 parts by weight component, said component (a) 100 parts by weight, coating a composition comprising only the substrate 2 at 130 ° C. The film is dried for 10 minutes to form a coating film 2 having a thickness of 10 μm, and the development time is twice as long as it is completely immersed in cyclopentanone at 23 ° C.
Similarly coating 2 is formed, exposure 50 mJ / cm ² to i-line exposure, the film remaining ratio after the development of the developing time at 23 ° C. in cyclopentanone 80% Component (B2): A compound that generates radicals by actinic radiation and satisfies the following conditions (iii) and (iv):
And (iii) except for solvent coating, and 20 parts by weight of tetraethylene glycol dimethacrylate, (B2) and 2 parts by mass of component alone, and the component (A) 100 parts by weight of a composition comprising only a substrate The film is dried at 130 ° C. for 2 minutes to form a coating film 3 having a thickness of 10 μm, and the development time is twice as long as it is completely dissolved by being immersed in cyclopentanone at 23 ° C.
Similarly, a coating film 3 was formed , i-line was exposed at an exposure amount of 300 mJ / cm ² , 350 mJ / cm ² and 400 mJ / cm ² , and development was performed on cyclopentanone at 23 ° C. for the above development time . The remaining film ratio after 80% or more and less than 90%,
(Iv) except for solvent coating, and 20 parts by weight of tetraethylene glycol dimethacrylate, (B2) and 2 parts by mass of component alone, and the component (A) 100 parts by weight of a composition comprising only a substrate The film is dried at 130 ° C. for 2 minutes to form a coating film 4 having a thickness of 10 μm, and the development time is twice as long as it is completely dissolved by being immersed in cyclopentanone at 23 ° C.
Similarly to form a coating film 4 is exposed to i-line at one of the exposure amount of ^{30mJ / cm 2, 60mJ / cm} 2, 80mJ / cm 2 and 90 mJ / cm ^2, the developing at 23 ° C. in cyclopentanone 20% or less residual film ratio after the development of the time Contains the following (A) component, (B1) component and (B2) component ,
The photosensitive resin composition which contains 0.01-1.5 mass part of said (B1) component, and 1-10 mass parts of said (B2) component with respect to 100 mass parts of said (A) component .
(A) component: at least one polymer of a polyimide and a polyimide precursor having a monovalent organic group having a carbon-carbon unsaturated double bond,
(B1) component: O-acyl oxime compound,
(B2) component: acylphosphine oxide compound or acyl dialkoxymethane compound The component (B1) is a compound represented by the following formula (21), and the component (B2) is selected from the group consisting of compounds represented by the following formulas (26), (27) and (28) The photosensitive resin composition according to claim 1, which is the above compound.

(In the formula (21), R ₁₁ represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group, and R ₁₂ represents Represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group, and R ₁₃ represents a substituted or unsubstituted benzoyl group, a substituted or unsubstituted fluorenyl group, a substituted or Represents an unsubstituted carbazolyl group.)

(In the formula (26), R ₁₇ , R ₁₈ and R ₁₉ each independently represents an alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.)

(In formula (27), R ₂₀ , R ₂₁ and R ₂₂ each independently represents an alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.)

(In formula (28), R _{23 to} R ₂₆ each independently represents an alkyl group having 1 to 20 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.) The component (A1) contains 0.1 to 0.5 parts by mass of the component (B1) and 1.5 to 9 parts by mass of the component (B2) with respect to 100 parts by mass of the component (A). The photosensitive resin composition of one term. The said (A) component is a polyimide precursor which has a structural unit represented by following formula (1), The photosensitive resin composition as described in any one of Claims 1-4.

(In the formula (1), A is any one of tetravalent organic groups represented by the following formulas (2a) to (2d), and B is a divalent organic group represented by the following formula (3). R ¹ and R ² are each independently a hydrogen atom or a monovalent organic group, and at least one of R ¹ and R ² is a monovalent organic group having the carbon-carbon unsaturated double bond. )

(In the above formula, X and Y each independently represent a divalent group or a single bond that is not conjugated to the benzene ring to which each is bonded.)

(In formula (3), R ^{3 to} R ¹⁰ each independently represent a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ^{3 to} R ¹⁰ represents a fluorine atom or a trifluoromethyl group. .) The photosensitive resin composition according to claim 5, wherein the polyimide precursor further has a structural unit represented by the following formula (19).

(In formula (19), D is a tetravalent organic group represented by the following formula (20), B is a divalent organic group represented by the above formula (3). R ¹ and R ² Are each independently a hydrogen atom or a monovalent organic group.)

(In the formula, Z represents an oxygen atom or a sulfur atom.) Applying and drying the photosensitive resin composition according to any one of claims 1 to 6 on a substrate to form a coating film;
Irradiating the coating film with an actinic ray to expose it in a pattern; and
Removing unexposed portions by development to obtain a patterned resin film;
A process for producing a cured pattern film comprising a step of heat-treating the patterned resin film. The electronic component which has a pattern cured film produced using the photosensitive resin composition as described in any one of Claims 1-6 as at least one of an interlayer insulation film layer and a surface protective film layer.