JP6414060B2 - Resin composition, pattern forming method using the same, and electronic component - Google Patents

Description

  The present invention relates to a resin composition, a pattern forming method using the resin composition, and an electronic component.

  With miniaturization of semiconductor integrated circuits, an interlayer insulating film called a low-k layer is required to reduce the dielectric constant. 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 properties such as thick film formability and high elastic modulus. However, by increasing the film thickness and increasing the elastic modulus, the stress after curing increases, and the warpage of the semiconductor wafer increases, which may cause problems when transporting or fixing the wafer. Development is desired.

  In order to reduce the stress while maintaining the high heat resistance and good mechanical properties of polyimide resin, it has been reported that it is effective to reduce the thermal expansion coefficient by making the polyimide skeleton a rigid and linear skeleton. Has been.

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 the resin film with respect to i-line is lowered and pattern formation cannot be performed. On the other hand, in order to increase the i-line transmittance of the coating film, there is a method using a polyimide precursor containing fluorine.
However, the cured film obtained after heat curing the fluorine-containing polyimide precursor has a drawback that the adhesion of the substrate to the silicon wafer is low (for example, Patent Documents 1 and 2).

  In order to give excellent adhesion to a silicon wafer, a resin composition using 3-isocyanatopropyltriethoxysilane has been reported (for example, Patent Document 3). However, since it has a highly reactive isocyanate group, there is a problem that the storage stability of the resin composition is deteriorated. In addition, the rigid polyimide precursor, which has a low CTE after curing, generates a stress with the silicon wafer when it is applied to the silicon wafer and heated before exposure (when it is made into a resin film). There is a problem that the film is easily peeled off from the silicon wafer.

  Moreover, in addition to the adhesiveness at the time of image development, the adhesiveness after hardening is also requested | required. If the adhesiveness after curing is poor, the cured film peels off from the substrate, causing a defect in the next process.

Japanese Patent No. 2826940 Japanese Patent No. 4144110 JP 11-338157 A

  In order to solve the above-mentioned problems, the present invention provides a resin composition in which the obtained cured film has low stress, excellent adhesion during development with a substrate, and excellent adhesion after curing in a developed film. Another object of the present invention is to provide a method for producing a cured pattern film using the resin composition.

（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価の有機基であり、
Ｒ^１及びＲ^２は、各々独立に、水素原子、１価の有機基、又は炭素炭素不飽和二重結合を有する基であり、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基である。

（式（２ｄ）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価の基又は単結合である。）

（式（３）中、Ｒ^３〜Ｒ^１０は、各々独立に、水素原子又は１価の有機基である。但し、Ｒ^３〜Ｒ^１０は、ハロゲン原子及びハロゲン原子を有する１価の有機基ではない。）

（式（４−１）中、Ｒ^１１は、各々独立に、炭素数１〜４のアルキル基であり、
Ｒ^１２は、各々独立に、水酸基又は炭素数１〜４のアルキル基であり、
ａは、１〜３の整数であり、
ｎは、１〜６の整数であり、
Ｒ^１３は、下記式（５）又は（６）の基である。）

（式（５）中、Ｒ^１４は、炭素数１〜１０のアルキル基又はヒドロキシアルキルシラン由来の１価の有機基である。
式（６）中、Ｒ^１５は、水素原子、炭素数１〜１０のアルキル基、アミノアルキルシラン由来の１価の有機基、又は複素環基である。
Ｒ^１４及びＲ^１５は、各々、置換基を有していてもよい。）

（式（４−２）中、Ｒ^１１は、各々独立に、炭素数１〜４のアルキル基であり、
Ｒ^１２は、各々独立に、水酸基又は炭素数１〜４のアルキル基であり、
ａは、１〜３の整数であり、
ｎは、１〜６の整数であり、
Ｒ^１３は、エポキシ基を有する有機基、又はジヒドロキシエチルアミノ基を有する有機基である。））
２．前記（ｂ）成分として、前記式（４−１）で表される化合物及び前記式（４−２）で表される化合物を含有する１に記載の樹脂組成物。
３．前記（ｃ）成分が、下記式（７）で表される化合物である１又は２に記載の樹脂組成物。

（式（７）中、Ｒ^１６〜Ｒ^２２は、各々独立に、水素原子又は１価の基である。）
４．前記（ａ）成分が、更に下記式（９）で表される構造単位を有する１〜３のいずれかに記載の樹脂組成物。

（式（９）中、Ｄは、下記式（１０）で表される４価の有機基であり、
Ｂ、Ｒ^１及びＲ^２は、前記式（１）と同じである。）

（式（１０）中、Ｚは、酸素原子又は硫黄原子である。）
５．（ａ）１〜４のいずれかに記載の樹脂組成物を基板上に塗布し乾燥して塗膜を形成する工程と、
（ｂ）前記工程（ａ）で形成される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、
（ｃ）前記露光部以外の未露光部を現像によって除去する工程と、
（ｄ）前記工程（ｃ）で得られるパターンを加熱処理してポリイミドパターンとする工程と、を有するパターン硬化膜の製造方法。
６．１〜４のいずれかに記載の樹脂組成物を硬化させた硬化膜。
７．６に記載の硬化膜を層間絶縁膜層及び／又は表面保護膜層として有する電子部品。According to the present invention, the following resin composition and the like are provided.
1. A resin composition containing (a) a polyimide precursor, (b) an alkoxysilane compound, (c) a photoinitiator and (d) a solvent,
The component (a) has a structural unit represented by the following formula (1),
The component (b) contains one or more of a compound represented by the following formula (4-1) and a compound represented by the following formula (4-2),
The component (c) is a resin composition containing an oxime ester compound.

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

(In Formula (2d), X and Y are each independently 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 are each independently a hydrogen atom or a monovalent organic group, provided that R ^{3 to} R ¹⁰ are a monovalent organic group having a halogen atom and a halogen atom. is not.)

(In formula (4-1), each R ¹¹ is independently an alkyl group having 1 to 4 carbon atoms,
R ¹² is each independently a hydroxyl group or an alkyl group having 1 to 4 carbon atoms,
a is an integer of 1 to 3,
n is an integer of 1 to 6,
R ¹³ is a group of the following formula (5) or (6). )

(In Formula (5), R < ¹⁴ > is a monovalent organic group derived from a C1-C10 alkyl group or hydroxyalkylsilane.
In formula (6), R ¹⁵ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a monovalent organic group derived from aminoalkylsilane, or a heterocyclic group.
R ¹⁴ and R ¹⁵ may each have a substituent. )

(In formula (4-2), each R ¹¹ is independently an alkyl group having 1 to 4 carbon atoms,
R ¹² is each independently a hydroxyl group or an alkyl group having 1 to 4 carbon atoms,
a is an integer of 1 to 3,
n is an integer of 1 to 6,
R ¹³ is an organic group having an epoxy group or an organic group having a dihydroxyethylamino group. ))
2. 2. The resin composition according to 1, which contains a compound represented by the formula (4-1) and a compound represented by the formula (4-2) as the component (b).
3. The resin composition according to 1 or 2, wherein the component (c) is a compound represented by the following formula (7).

(In formula (7), R ^{16 to} R ²² are each independently a hydrogen atom or a monovalent group.)
4). The resin composition according to any one of 1 to 3, wherein the component (a) further has a structural unit represented by the following formula (9).

(In formula (9), D is a tetravalent organic group represented by the following formula (10),
B, R ¹ and R ² are the same as those in the formula (1). )

(In Formula (10), Z is an oxygen atom or a sulfur atom.)
5. (A) applying the resin composition according to any one of 1 to 4 on a substrate and drying to form a coating film;
(B) a step of irradiating the coating film formed in the step (a) with an actinic ray to expose it in a pattern;
(C) removing unexposed portions other than the exposed portions by development;
(D) A process for producing a cured pattern film, comprising a step of heat-treating the pattern obtained in the step (c) to form a polyimide pattern.
The cured film which hardened the resin composition in any one of 6.1-4.
An electronic component having the cured film according to 7.6 as an interlayer insulating film layer and / or a surface protective film layer.

  According to the present invention, the obtained cured film has low stress, and has excellent adhesion at the time of development with the substrate and excellent adhesion after curing in the post-development film, and the resin composition. A method for producing a patterned cured film is provided.

It is a schematic sectional drawing of one Embodiment of the semiconductor device using the resin composition of this invention.

(Resin composition)
The resin composition of the present invention contains (a) a polyimide precursor, (b) an alkoxysilane compound, (c) a photoinitiator and (d) a solvent,
The component (a) has a structural unit represented by the following formula (1),
The component (b) contains one or more of a compound represented by the following formula (4-1) and a compound represented by the following formula (4-2),
The component (c) contains an oxime ester compound.

（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価の有機基であり、
Ｒ^１及びＲ^２は、各々独立に、水素原子、１価の有機基、又は炭素炭素不飽和二重結合を有する基であり、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基である。

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

（式（２ｄ）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価の基又は単結合である。）

（式（３）中、Ｒ^３〜Ｒ^１０は、各々独立に、水素原子又は１価の有機基である。但し、Ｒ^３〜Ｒ^１０は、ハロゲン原子及びハロゲン原子を有する１価の有機基ではない。）

(In Formula (2d), X and Y are each independently 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 are each independently a hydrogen atom or a monovalent organic group, provided that R ^{3 to} R ¹⁰ are a monovalent organic group having a halogen atom and a halogen atom. is not.)

（式（４−１）中、Ｒ^１１は、各々独立に、炭素数１〜４のアルキル基であり、
Ｒ^１２は、各々独立に、水酸基又は炭素数１〜４のアルキル基であり、
ａは、１〜３の整数であり、
ｎは、１〜６の整数であり、
Ｒ^１３は、下記式（５）又は（６）の基である。）

（式（５）中、Ｒ^１４は、炭素数１〜１０のアルキル基又はヒドロキシアルキルシラン由来の１価の有機基である。
式（６）中、Ｒ^１５は、水素原子、炭素数１〜１０のアルキル基、アミノアルキルシラン由来の１価の有機基、又は複素環基である。
Ｒ^１４及びＲ^１５は、各々、置換基を有していてもよい。）

(In formula (4-1), each R ¹¹ is independently an alkyl group having 1 to 4 carbon atoms,
R ¹² is each independently a hydroxyl group or an alkyl group having 1 to 4 carbon atoms,
a is an integer of 1 to 3,
n is an integer of 1 to 6,
R ¹³ is a group of the following formula (5) or (6). )

(In Formula (5), R < ¹⁴ > is a monovalent organic group derived from a C1-C10 alkyl group or hydroxyalkylsilane.
In formula (6), R ¹⁵ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a monovalent organic group derived from aminoalkylsilane, or a heterocyclic group.
R ¹⁴ and R ¹⁵ may each have a substituent. )

（式（４−２）中、Ｒ^１１は、各々独立に、炭素数１〜４のアルキル基であり、
Ｒ^１２は、各々独立に、水酸基又は炭素数１〜４のアルキル基であり、
ａは、１〜３の整数であり、
ｎは、１〜６の整数であり、
Ｒ^１３は、エポキシ基を有する有機基、又はジヒドロキシエチルアミノ基を有する有機基である。））

(In formula (4-2), each R ¹¹ is independently an alkyl group having 1 to 4 carbon atoms,
R ¹² is each independently a hydroxyl group or an alkyl group having 1 to 4 carbon atoms,
a is an integer of 1 to 3,
n is an integer of 1 to 6,
R ¹³ is an organic group having an epoxy group or an organic group having a dihydroxyethylamino group. ))

Hereinafter, each component will be described.
(A) Component: Polyimide precursor The polyimide precursor used by this invention has a structural unit represented by the said Formula (1). A in the formula (1) is a structure derived from tetracarboxylic dianhydride used as a raw material for the polyimide precursor. In order to reduce the stress of the cured film obtained from the resin composition, A is any one of tetravalent organic groups represented by the following formulas (2a) to (2d).

In formula (2d), X and Y are each independently a divalent group or a single bond that is not conjugated to the benzene ring to which each is bonded. Examples of the “divalent group that is not conjugated with the benzene ring to which each is bonded” include —O—, —C (CH ₃ ) ₂ —, —C (CH ₃ ) (CF ₃ ) —, —C (CF ₃ ) ₂ —, —Si (CH ₃ ) ₂ — and the like.

  Examples of tetracarboxylic dianhydrides that give tetravalent organic groups represented by the formulas (2a) to (2d) include pyromellitic dianhydride and 2,3,6,7-naphthalenetetracarboxylic dianhydride. 4,4′-biphenyltetracarboxylic dianhydride, 9,9′-dimethyl-2,3,6,7-xanthenetetracarboxylic dianhydride, represented by the following formulas (11) to (17) A tetracarboxylic dianhydride is mentioned.

  At the time of polymerization of the polyimide precursor, any one of these may be used alone, or two or more kinds of tetracarboxylic dianhydrides may be used in combination. Of these, pyromellitic dianhydride, 4,4′-biphenyltetracarboxylic dianhydride, tetracarboxylic acid dianhydrides represented by the formulas (11) and (13) are used from the viewpoint of reducing the thermal expansion of the cured film. It is preferable to use an anhydride, more preferably pyromellitic dianhydride, 4,4′-biphenyltetracarboxylic dianhydride, tetracarboxylic dianhydride represented by the formula (11), It is particularly preferable to use merit acid dianhydride and 4,4′-biphenyltetracarboxylic dianhydride.

B in Formula (1) is a structure derived from a diamine used as a raw material for the polyimide precursor. From the viewpoint of low stress and i-line transmittance, B is a divalent organic group represented by the following formula (3).

In formula (3), R ^{3 to} R ¹⁰ are each independently a hydrogen atom or a monovalent organic group. However, the case where it is a monovalent organic group having a halogen atom and a halogen atom is excluded. In the case of a halogen atom or a monovalent organic group containing a halogen atom, when the cured film is subjected to plasma treatment, the bond between carbon-halogen atoms may be broken and the cured film may be deteriorated.
Examples of the monovalent organic group include an alkyl group having 1 to 20 carbon atoms (such as a methyl group) and an alkoxy group having an alkyl group having 1 to 20 carbon atoms (such as a methoxy group).

  Examples of the diamine used as a raw material for the polyimide precursor include 2,2′-diaminobenzidine, 3,3′-diaminobenzidine, 2,2 ′, 3,3′-tetramethylbenzidine, and 2,2′-dimethoxybenzidine. 3,3′-dimethoxybenzidine and the like can be used.

  These may be used independently at the time of superposition | polymerization of a polyimide precursor, and may use it in combination of 2 or more types of diamine. Of these, 2,2'-diaminobenzidine and 3,3'-diaminobenzidine are preferred, and 2,2'-diaminobenzidine is more preferred from the viewpoint of reducing stress.

In Formula (1), R ¹ and R ² are each independently a hydrogen atom, a monovalent organic group, or a group having a carbon-carbon unsaturated double bond. At least one of R ¹ and R ² is a group having a carbon-carbon unsaturated double bond.

Examples of the monovalent organic group as R ¹ and R ² include an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms.

Examples of the group having a carbon-carbon unsaturated double bond as R ¹ and R ² include an acryloxyalkyl group having 1 to 10 carbon atoms in the alkyl group and a methacryloxyalkyl group. The polyimide precursor has a monovalent organic group having a carbon-carbon unsaturated double bond at least in part, so that it is combined with a compound that generates radicals upon irradiation with actinic rays (for example, i-line exposure), and radical polymerization. It is possible to crosslink between the molecular chains by the above, and it becomes easy to obtain a negative resin composition.

  Specific examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-decyl. Group, n-dodecyl group and the like.

Specific examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group.
Examples of the acryloxyalkyl group having an alkyl group having 1 to 10 carbon atoms include acryloxyethyl group, acryloxypropyl group, acryloxybutyl group and the like.

  Examples of the methacryloxyalkyl group having an alkyl group having 1 to 10 carbon atoms include a methacryloxyethyl group, a methacryloxypropyl group, and a methacryloxybutyl group.

As a method of imparting photosensitivity to a polyimide precursor, a method of adding a tertiary amine compound having a carbon-carbon unsaturated double bond to a corresponding polyamic acid is known. However, the carboxyl group in the polyamic acid and the tertiary amine form an ionic bond, and the state of the ionic bond may change due to the influence of pH and moisture of the varnish, which may reduce the storage stability. Therefore, R ¹ and R ² are preferably not a hydrogen atom but a group introduced by an ester bond. Among these, from the viewpoint of good photosensitivity, R ¹ and R ² are preferably an acryloxyethyl group, an acryloxybutyl group, a methacryloxyethyl group, or a methacryloxyethyl group introduced by an ester bond.

  From the viewpoint of lowering the stress of the obtained cured film, it is preferable that the polyimide precursor has a structural unit represented by the formula (1) of 10 mol% or more with respect to all the structural units of the polyimide precursor, and 20 mol% or more. More preferably.

（式（９）中、Ｄは、下記式（１０）で表される４価の有機基であり、
Ｂ、Ｒ^１及びＲ^２は、前記式（１）と同じである。）

（式（１０）中、Ｚは、酸素原子（エーテル結合：−Ｏ−）又は硫黄原子（スルフィド結合：−Ｓ−）である。）The polyimide precursor used in the resin composition of the present invention further has a structural unit represented by the following formula (9) from the viewpoint of improving i-line transmittance, improving adhesion after curing, and improving mechanical properties. You may do it.

(In formula (9), D is a tetravalent organic group represented by the following formula (10),
B, R ¹ and R ² are the same as those in the formula (1). )

(In Formula (10), Z is an oxygen atom (ether bond: -O-) or a sulfur atom (sulfide bond: -S-).)

  Examples of tetracarboxylic dianhydrides that give the structure of formula (10) include 4,4'-oxydiphthalic dianhydride and thioether diphthalic anhydride. When synthesizing the polyimide precursor, these may be used alone or in combination of two. From the viewpoint of adhesion after curing, 4,4'-oxydiphthalic dianhydride is preferably used.

  When the polyimide precursor has both the structural unit represented by the formula (1) and the structural unit represented by the formula (9), the polyimide precursor is copolymerized. Examples of the copolymer include a block copolymer and a random copolymer, but are not particularly limited.

  In the polyimide precursor having the structural unit represented by the formula (1) and the structural unit represented by the formula (9), from the viewpoint of achieving both low stress and good adhesion, the formula (1) and the formula The molar ratio of [9] [formula (1) / formula (9)] is preferably 1/9 to 9/1, more preferably 2/8 to 8/2, and 2/8 to More preferably, it is 7/3.

  The polyimide precursor of component (a) may have a structural unit other than the structural unit represented by formula (1) and the unit represented by formula (9). Examples of the tetracarboxylic dianhydride that gives a polyimide precursor having a structural unit other than the structural unit represented by the formula (1) and the unit represented by the formula (9) include 3,3 ′, 4,4, for example. '-Benzophenonetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 4,4'-[isopropylidenebis [(p-phenylene) oxy]] diphthalic acid 1,2: 1 ', 2'-dianhydride etc. are mentioned. Examples of the diamine that gives a polyimide precursor having a structural unit other than the structural unit represented by the formula (1) and the unit represented by the formula (9) include 4,4′-oxydianiline, 4,4 ′. -Diaminodiphenylmethane, 1,4-cyclohexanediamine, 1,3′-bis (3-aminophenoxy) benzene and the like.

  From the viewpoint of reducing stress, these tetracarboxylic dianhydrides and diamines are preferably 20 mol% or less, preferably 10 mol% or less, based on the total amount of tetracarboxylic dianhydrides and diamines used as raw materials. Are more preferable, and it is particularly preferable to use only a tetracarboxylic dianhydride and a diamine which give the structures of the formulas (1) and (9).

As for the molecular weight of the polyimide precursor 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, and if it is greater 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 a risk.
In addition, a weight average molecular weight can be measured by the gel permeation chromatography method, and is calculated | required by converting using a standard polystyrene calibration curve.

  The resin composition of the present invention preferably contains 20 to 60 mass% of the polyimide precursor of component (a), more preferably 25 to 55 mass%, more preferably 30 to 55 mass% in the total resin composition. It is more preferable to contain.

  The polyimide precursor of component (a) can be synthesized by a conventionally known method.

（式（４−１）中、Ｒ^１１は、炭素数１〜４のアルキル基であり、
Ｒ^１２は、各々独立に、水酸基又は炭素数１〜４のアルキル基であり、
ａは、１〜３の整数であり、
ｎは、１〜６の整数であり、
Ｒ^１３は、下記式（５）又は（６）の基である。）

（式（５）中、Ｒ^１４は、炭素数１〜１０のアルキル基又はヒドロキシアルキルシラン由来の１価の有機基である。
式（６）中、Ｒ^１５は、水素原子、炭素数１〜１０のアルキル基、アミノアルキルシラン由来の１価の有機基、又は複素環基である。
Ｒ^１４及びＲ^１５は、各々、置換基を有していてもよい。）(B) Component: Alkoxysilane Compound The alkoxysilane compound (b) is used as a component that improves the adhesion between the film and the substrate.
The resin composition of this invention contains the compound represented by (b1) following formula (4-1) as a (b) component from a viewpoint of improving the adhesiveness to the base material of the cured film obtained. Is preferred.

(In formula (4-1), R ¹¹ is an alkyl group having 1 to 4 carbon atoms,
R ¹² is each independently a hydroxyl group or an alkyl group having 1 to 4 carbon atoms,
a is an integer of 1 to 3,
n is an integer of 1 to 6,
R ¹³ is a group of the following formula (5) or (6). )

(In Formula (5), R < ¹⁴ > is a monovalent organic group derived from a C1-C10 alkyl group or hydroxyalkylsilane.
In formula (6), R ¹⁵ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a monovalent organic group derived from aminoalkylsilane, or a heterocyclic group.
R ¹⁴ and R ¹⁵ may each have a substituent. )

（式（４−２）中、Ｒ^１１は、各々独立に、炭素数１〜４のアルキル基であり、
Ｒ^１２は、各々独立に、水酸基又は炭素数１〜４のアルキル基であり、
ａは、１〜３の整数であり、
ｎは、１〜６の整数であり、
Ｒ^１３は、エポキシ基を有する有機基、又はジヒドロキシエチルアミノ基を有する有機基である。）Moreover, it is preferable that the resin composition of this invention contains the compound represented by (b2) following formula (4-2) as (b) component.

(In formula (4-2), each R ¹¹ is independently an alkyl group having 1 to 4 carbon atoms,
R ¹² is each independently a hydroxyl group or an alkyl group having 1 to 4 carbon atoms,
a is an integer of 1 to 3,
n is an integer of 1 to 6,
R ¹³ is an organic group having an epoxy group or an organic group having a dihydroxyethylamino group. )

  It is preferable to use the component (b1) and the component (b2) together in terms of increasing the adhesiveness at the time of development with the substrate and the adhesiveness after curing in the post-development film.

  The resin composition of this invention can express the adhesiveness to the favorable board | substrate when it is set as a cured film by containing (b1) component. This is because in the heat curing step of the resin film, the isocyanate protecting group of the compound represented by the formula (4-1) is eliminated, the highly reactive isocyanate group is regenerated, and the polymer (polyimide precursor) terminal carboxyl is recovered. It is thought to react with acids and amines to form chemical bonds.

  Moreover, the resin composition of this invention can express favorable storage stability by containing (b1) component. This is presumably because the protected isocyanate of the compound represented by formula (4-1) is in a low-reactive state in which the protective group is not eliminated before the heat curing step.

（式（２１）中、Ｒ^２９は、炭素数１〜４のアルキル基であり、
Ｒ^３０は、各々独立に、水酸基又は炭素数１〜４のアルキル基であり、
ｂは、１〜３の整数であり、
Ｒ^２８は、炭素数１〜６のアルキレン基である。）The compound represented by the formula (4-1) is obtained by mixing the compound represented by the formula (21) with a compound having a hydroxyl group or an amino group and causing an addition reaction.

(In the formula (21), R ²⁹ is an alkyl group having 1 to 4 carbon atoms,
R ³⁰ is each independently a hydroxyl group or an alkyl group having 1 to 4 carbon atoms,
b is an integer of 1 to 3,
R ²⁸ is an alkylene group having 1 to 6 carbon atoms. )

  Examples of the compound represented by the formula (21) include 1-isocyanatomethyltrimethylsilane, 1-isocyanatomethyltriethylsilane, 1-isocyanatemethyltripropylsilane, 1-isocyanatemethyltributylsilane, 1-isocyanatomethyltrimethylsilane. Methoxysilane, 1-isocyanatomethyldimethoxymethylsilane, 1-isocyanatomethylmethoxydimethylsilane, 1-isocyanatomethyltriethoxysilane, 1-isocyanatomethyltripropoxysilane, 1-isocyanatomethyltributoxysilane, Isocyanate methyldiethoxyethylsilane, 3-isocyanatopropyltrimethylsilane, 3-isocyanatopropyltriethylsilane, 3-isocyanatopropyltrimethoxysilane, 3- Sodium propyldimethoxymethylsilane, 3-isocyanatopropylmethoxydimethylsilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyldiethoxyethylsilane, 3-isocyanatopropylethoxydiethylsilane, 6-isocyanatohexyltri Methoxysilane, 6-isocyanatohexyldimethoxymethylsilane, 6-isocyanatohexylmethoxydimethylsilane, 6-isocyanatohexyltriethoxysilane, 6-isocyanatohexyldiethoxyethylsilane, 6-isocyanatohexylethoxydiethylsilane, etc. From the viewpoint of availability, 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane are preferred. .

（式（２２）中、Ｒは、−Ｒ^２８−Ｓｉ（ＯＲ^２９）_ｂ（Ｒ^３０）_３−ｂであり、
Ｒ^２８、Ｒ^２９、Ｒ^３０及びｂは、式（２１）と同じであり、
Ｒ’は、炭素数１〜１０のアルキル基である。）In the compound of the formula (4-1), the compound in which R ¹³ is represented by the formula (5) can be obtained by reacting the compound of the formula (21) with a compound having a hydroxyl group and a compound having a hydroxyalkylsilane. This reaction formula is shown in the following formula (22).

(In the formula (22), R _{^{is, -R 28 -Si (OR 29)}} b (R 30) is a _3-b,
R ²⁸ , R ²⁹ , R ³⁰ and b are the same as in formula (21),
R ′ is an alkyl group having 1 to 10 carbon atoms. )

When a compound in which R ′ is an alkyl group having 1 to 10 carbon atoms is reacted with formula (21), a compound in which R ¹⁴ in formula (5) is an alkyl group having 1 to 10 carbon atoms is obtained. Examples of such a compound having 1 to 10 carbon atoms having a hydroxyl group include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, t-butanol, hexanol, heptanol, octanol, nonal, decanol, 2- Methyl-1-hexanol, 3-methyl-1-hexanol, 4-methyl-1-hexanol, 5-methyl-1-hexanol, 2-ethyl-1-hexanol, 3-ethyl-1-hexanol, 4-ethyl- Examples include 1-hexanol, 2,2-dimethyl-1-propanol, and cyclohexanol.

When the hydroxyalkylsilane compound is reacted with the compound of formula (21), a compound in which R ¹⁴ in formula (5) has an organic group derived from hydroxyalkylsilane is obtained. Examples of the hydroxyalkylsilane compound include bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, N, N-bis (2-hydroxyethyl) -N, N-bis (trimethoxysilylpropyl) ethylenediamine, N- (Hydroxymethyl) -N-methylaminopropyltrimethoxysilane, 7-triethoxysilylpropoxy-5-hydroxyflavone, N- (3-triethoxysilylpropyl) -4-hydroxybutyramide, 2-hydroxy-4- ( 3methyldiethoxysilylpropoxy) diphenyl ketone, 1,3-bis (4-hydroxybutyl) tetramethyldisiloxane, 3- (N-acetyl-4-hydroxypropyloxy) propyltriethoxysilane, hydroxymethyltriethoxysilane, etc. Is illustrated, while Also bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane are preferred.

（式（２３）中、Ｒは、−Ｒ^２８−Ｓｉ（ＯＲ^２９）_ｂ（Ｒ^３０）_３−ｂであり、
Ｒ^２８、Ｒ^２９、Ｒ^３０及びｂは、式（２１）と同じであり、
Ｒ’は、水素原子又は炭素数１〜１０のアルキル基である。）In the compound of the formula (4-1), the compound in which R ¹³ is represented by the formula (6) is a compound of the formula (21), ammonia, a compound having 1 to 10 carbon atoms having an amino group, an aminoalkylsilane compound Alternatively, it can be obtained by reacting a heterocyclic compound having an amino group. This reaction formula is shown in the following formula (23).

(In the formula (23), R _{^{is, -R 28 -Si (OR 29)}} b (R 30) is a _3-b,
R ²⁸ , R ²⁹ , R ³⁰ and b are the same as in formula (21),
R ′ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. )

When a compound in which R ′ is a hydrogen atom is reacted with formula (21), a compound in which R ^{15 in} formula (6) is a hydrogen atom is obtained. An example of such a compound is ammonia.
When a compound in which R ′ is an alkyl group having 1 to 10 carbon atoms is reacted with formula (21), a compound in which R ^{15 in} formula (6) is an alkyl group having 1 to 10 carbon atoms is obtained. Examples of the compound having 1 to 10 carbon atoms having an amino group include aminomethane, aminoethane, aminopropane, aminobutane, aminopentane, aminohexane, aminoheptane, aminooctane, aminononane, aminodecane, and 2-ethylaminohexane.

When the aminoalkylsilane compound is reacted with the formula (21), a compound in which R ^{15 in the} formula (6) has an aminoalkylsilane-derived organic group is obtained. Examples of aminoalkylsilane compounds include 4-aminobutyltriethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysiloxane, N- (2-aminoethyl) -3-aminopropylmethyl-dimethoxysilane, N- ( 2-aminoethyl) -4-aminopropylmethyl-triethoxysilane and the like.

When the heterocyclic compound having an amino group is reacted with the compound of the formula (21), a compound in which R ¹⁵ of the formula (6) is a heterocyclic group is obtained. Examples of the heterocyclic compound having an amino group include 5-aminotetrazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 4-aminopyridine, 2-aminopyridine, 3 -Aminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2-aminothiazole, 2-aminobenzothiazole and the like.

  Reaction of Formula (22) and (23) may be made to react at room temperature, or you may make it react in the temperature range between 50 to 100 degreeC. Further, the raw materials may be directly mixed or a solvent such as dimethylformamide, 1,2-diethoxyethane, N-methylpyrrolidone may be used.

In the resin composition of the present invention, the component (b1) preferably contains at least one of the following compounds from the viewpoint of providing better adhesion and better storage stability.

  As content of (b1) component, 0.1-20 mass parts is preferable with respect to 100 mass parts of (a) component, 1-10 mass parts is more preferable, and 1-6 are still more preferable. When it is 0.1 part by mass or more, sufficient adhesion to the substrate can be imparted, and when it is 20 parts by mass or less, problems such as an increase in viscosity during storage at room temperature can be further suppressed.

  The resin composition of the present invention preferably contains the component (b2) from the viewpoint of improving the adhesion between the film during development and the silicon wafer.

  By containing the component (b2), the epoxy group or the hydroxyl group reacts with the carboxyl group or amino group present at the terminal in the component (a) at the stage of performing the pre-exposure heating. It is thought that it has peeling of.

  As the compound used as the component (b2), γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bis (2- Hydroxyethyl) -3-aminopropyl-triethoxysilane. Particularly preferred is bis (2-hydroxyethyl) -3-aminopropyl-triethoxysilane.

  As content of (b2) component, 0.1-20 mass parts is preferable with respect to 100 mass parts of (a) component, 1-10 mass parts is more preferable, and 1-3 are still more preferable. When it is 0.1 part by mass or more, sufficient adhesion to the substrate can be imparted, and when it is 20 parts by mass or less, problems such as an increase in viscosity during storage at room temperature can be further suppressed.

The component (b1) and the component (b2) may be used alone or in combination.
When using together, 0.1-20 mass parts is preferable with respect to 100 mass parts of (a) component, as for content of (b1) component, 1-10 mass parts is more preferable, and 1-3 are still more preferable. 0.1-20 mass parts is preferable with respect to 100 mass parts of (a) component, as for content of (b2) component, 1-10 mass parts is more preferable, and 1-3 are still more preferable. 0.1-20 mass parts is preferable with respect to 100 mass parts of (a) component, as for content which combined (b1) component and (b2) component, 1-10 mass parts is more preferable, and 3-6 are further. preferable. When it is 0.1 part by mass or more, sufficient adhesion to the substrate can be imparted, and when it is 20 parts by mass or less, problems such as an increase in viscosity during storage at room temperature can be further suppressed.

Other alkoxysilane compounds In addition, in order to improve the adhesiveness to the silicon substrate etc. after hardening in the resin composition of this invention, the alkoxysilane compounds other than the above may be included. As alkoxysilane compounds other than the above, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltri Methoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, triethoxysilylpropylethylcarbamate, 3- (triethoxysilyl) propyl Succinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutane Isopropylidene) propylamine, and the like.

  In the case of containing the alkoxysilane compound, the content is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polyimide precursor from the viewpoint of adhesion after curing, and 0.5 to 15 It is more preferable to set it as a mass part, and it is still more preferable to set it as 0.5-10 mass parts.

（式（７）中、Ｒ^１６〜Ｒ^２２は、各々独立に、水素原子又は１価の基である。）(C) Component: Photoinitiator (c) A component contains an oxime ester compound. Specifically, a compound having a structure represented by the formula (7) is preferable.

(In formula (7), R ^{16 to} R ²² are each independently a hydrogen atom or a monovalent group.)

Specifically, R ¹⁶ represents a phenyl group (an alkyl group having 1 to 10 carbon atoms, a phenyl group, a halogen atom, an alkoxy group having 1 to 10 carbon atoms and an alkyl mercapto group, or an alkyl group having 1 to 10 carbon atoms. One or more dialkylamino groups, etc.), an alkyl group having 1 to 20 carbon atoms (provided that the alkyl group has 2 to 20 carbon atoms, one or more oxygen atoms between main chain carbon atoms) And / or may be substituted with one or more hydroxyl groups), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, or a benzoyl group (however, having 1 to 6 carbon atoms) An alkyl group, a phenyl group, an alkoxyl group, a thioether group, a dialkylamino group, etc.), an alkoxycarbonyl group having 2 to 12 carbon atoms (provided that the alkoxyl group has 2 carbon atoms) In the case of ˜11, it may have one or more oxygen atoms between main chain carbon atoms and / or may be substituted with one or more hydroxyl groups), a cyano group, a nitro group, or a carbon number of 1 to 4 A haloalkyl group, an alkylsulfinyl group having 1 to 6 carbon atoms and an alkylsulfonyl group, an arylsulfinyl group and an arylsulfonyl group (wherein the aryl group is an aryl group having 6 to 12 carbon atoms, and an alkyl group having 1 to 12 carbon atoms) Which may be substituted), an alkoxysulfonyl group having 1 to 6 carbon atoms, an aryloxysulfonyl group having 6 to 10 carbon atoms, or a diphenylphosphinoyl group.

R ¹⁷ is an alkanoyl group having 2 to 12 carbon atoms (provided that the alkanoyl group may be substituted with one or more halogen atoms or a cyano group), α, β 4 to 6 carbon atoms having no unsaturated carbonyl structure. Alkenoyl group, benzoyl group (however, it may be substituted with an alkyl group having 1 to 6 carbon atoms, phenyl group, alkoxyl group, thioether group or dialkylamino group), alkoxycarbonyl group having 2 to 6 carbon atoms, phenoxycarbonyl One of the groups (which may be substituted with one or more alkyl groups having 1 to 6 carbon atoms or a halogen atom).

R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group (however, a hydroxyl group, a mercapto group) Group, an alkoxyl group having 1 to 12 carbon atoms and an alkyl mercapto group (provided that at least one hydrogen atom in the alkyl chain is a hydroxyl group, a mercapto group, a cyano group, an alkoxyl group having 1 to 4 carbon atoms, a carbon number of 3 -6 alkenyloxy group, 2-cyanoethoxy group, 2- (alkoxycarbonyl) ethoxy group having 4 to 7 carbon atoms, alkylcarbonyloxy group having 2 to 5 carbon atoms, phenylcarbonyloxy group, carboxyl group, 2 carbon atoms An alkoxylcarbonyl group having 5 to 5 carbon atoms and one or more oxygen atoms between main chain carbon atoms having 2 to 6 carbon atoms A silyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, or an alkoxyl group having 2 to 12 carbon atoms. A carbonyl group (provided that when the alkoxyl group has 2 to 11 carbon atoms, the alkoxyl group has one or more oxygen atoms between main chain carbon atoms and / or is substituted with one or more hydroxyl groups) Or a phenoxycarbonyl group, a phenoxy group, and a phenylthio group (provided that at least one hydrogen atom on the phenyl ring is a hydroxyl group, an alkoxyl group having 1 to 6 carbon atoms, or an alkyl mercapto group having 1 to 6 carbon atoms). An alkyl group having 1 to 12 carbon atoms, a carboxyl group, a hydroxymethyloxycarbonyl group, a hydroxyethyloxycarbonyl group, Optionally substituted with either a droxyethyloxy group or a hydroxypropyloxy group), an alkylsulfinyl group having 1 to 6 carbon atoms and an alkylsulfonyl group, an arylsulfinyl group and an arylsulfonyl group (provided that the aryl group is a carbon atom) An aryl group having 6 to 12 carbon atoms, which may be substituted with an alkyl group having 1 to 12 carbon atoms), an alkoxysulfonyl group having 1 to 6 carbon atoms, an aryloxysulfonyl group having 6 to 10 carbon atoms, and a carbon number Any one of dialkylamino groups having two alkyl groups having 1 to 10. Among them, from the viewpoint of sensitivity, an alkyl mercapto group having 1 to 12 carbon atoms (provided that at least one hydrogen atom in the alkyl chain is A hydroxyl group, a mercapto group, a cyano group, an alkoxyl group having 1 to 4 carbon atoms, an alkenyloxy group having 3 to 6 carbon atoms, 2- Anoethoxy group, C4-C7 2- (alkoxycarbonyl) ethoxy group, C2-C5 alkylcarbonyloxy group, phenylcarbonyloxy group, carboxyl group, C2-C5 alkoxylcarbonyl group, main chain carbon A C2-C6 alkoxyl group having one or more oxygen atoms between atoms, a C2-C8 alkylcarbonyloxy group, and a phenyl group (which may be substituted), a phenylthio group (however, At least one hydrogen atom on the phenyl ring is a hydroxyl group, an alkoxyl group having 1 to 6 carbon atoms, an alkyl mercapto group having 1 to 6 carbon atoms, an alkyl group having 1 to 12 carbon atoms, a carboxyl group, hydroxymethyloxy Carbonyl group, hydroxyethyloxycarbonyl group, hydroxyethyloxy group, hydroxypropyl May be substituted with any of the group) it is preferred.

R ¹⁶ is preferably an alkyl group having 1 to 10 carbon atoms. In addition, any one of R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² is an alkyl mercapto group having 1 to 12 carbon atoms (provided that at least one hydrogen atom in the alkyl chain is a hydroxyl group or a mercapto group) , Cyano group, alkoxy group having 1 to 4 carbon atoms, alkenyloxy group having 3 to 6 carbon atoms, 2-cyanoethoxy group, 2- (alkoxycarbonyl) ethoxy group having 4 to 7 carbon atoms, and 2 to 5 carbon atoms An alkylcarbonyloxy group, a phenylcarbonyloxy group, a carboxyl group, an alkoxylcarbonyl group having 2 to 5 carbon atoms, an alkoxyl group having 2 to 6 carbon atoms having one or more oxygen atoms between main chain carbon atoms, and 2 to 2 carbon atoms. 8 alkylcarbonyloxy groups, which may be substituted with any of phenyl groups) or phenylthio groups (provided that at least one of them on the phenyl ring) The above hydrogen atom is a hydroxyl group, an alkoxyl group having 1 to 6 carbon atoms, an alkyl mercapto group having 1 to 6 carbon atoms, an alkyl group having 1 to 12 carbon atoms, a carboxyl group, a hydroxymethyloxycarbonyl group, or hydroxyethyloxycarbonyl. And may be substituted with any one of a group, a hydroxyethyloxy group, and a hydroxypropyloxy group).

（式（８）中、芳香環は置換基を有していてもよい。）Furthermore, it is more preferable R ¹⁶ is a hexyl group. More preferably, R ¹⁸ , R ¹⁹ , R ²⁰ and R ¹⁷ are hydrogen atoms and R ¹⁵ is a phenylthio group. Among these, a compound represented by the formula (8) (1,2-octanedione, 1- [4- (phenylthio) phenyl], 2- (O-benzoyloxime)) is more preferable.

(In Formula (8), the aromatic ring may have a substituent.)

  As content of (c) component, it is preferable that it is 0.1-20 mass parts with respect to 100 mass parts of polyimide precursor which is (a) component, and it is 0.1-15 mass parts. More preferably, it is 0.5-10 mass parts, More preferably, it is 0.5-5 mass parts, It is very preferable that it is 1-5 mass parts. When the blending amount is 0.1 parts by mass or more, crosslinking of the exposed part proceeds more sufficiently and the photosensitive properties (sensitivity, resolution) tend to be better, and when it is 20 parts by mass or less, the cured film The heat resistance of can be made better.

  The resin composition of the present invention is excellent in photosensitive characteristics by combining the component (a) and the component (c), and the stress of the cured film to be formed becomes low. In particular, when a polyimide precursor having a structural unit represented by the formula (1) is used as the component (a) and a compound represented by the formula (7) is used as the component (c), it is represented by the formula (7). Since the compound exhibits high activity particularly when irradiated with an electron beam such as i-line, good photosensitive characteristics can be realized. Furthermore, when it becomes a polyimide by heat treatment, it has a feature of exhibiting low stress due to its rigid skeleton.

(D) Component: Solvent As the (d) component, a polar solvent that completely dissolves the polyimide precursor as the component (a) is preferable. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphate triamide, γ-butyrolactone, δ-valerolactone, γ-valerolactone Cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, propylene carbonate, ethyl lactate, 1,3-dimethyl-2-imidazolidinone, N, N′-dimethylpropylene urea. These may be used alone or in combination of two or more.

  The solvent is preferably contained in the resin composition in an amount of 40 to 80% by mass, more preferably 45 to 75% by mass, and still more preferably 45 to 70% by mass.

  You may mix | blend an addition polymerizable compound with the resin composition of this invention as needed. Examples of the addition polymerizable compound include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, and trimethylolpropane. Triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate , Pentaerythritol triacrylate, pentaerythritol tetraacrylate, Intererythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1,3-acryloyloxy-2 -Hydroxypropane, 1,3-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide and the like. These may be used alone or in combination of two or more.

  In the case of containing an addition polymerizable compound, the content may be 1 to 100 parts by mass with respect to 100 parts by mass of the polyimide precursor from the viewpoint of solubility in a developer and heat resistance of a cured film to be obtained. Preferably, it is 1-75 mass parts, More preferably, it is 1-50 mass parts.

  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, N-phenyl-2-naphthylamine, cuperone, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines and the like can be mentioned. These may be used alone or in combination of two or more.

  In the case of containing a radical polymerization inhibitor or a radical polymerization inhibitor, the content is preferably from about 0.1 parts by mass with respect to 100 parts by mass of the polyimide precursor from the viewpoint of the storage stability of the resin composition and the heat resistance of the resulting cured film. It is preferably 01 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and still more preferably 0.05 to 5 parts by mass.

  In addition, the resin composition of the present invention has, for example, 90% by weight or more, 95% by weight or more, 98% by weight or more, and 100% by weight of the above components (a) to (d) and optionally other components described above. It may consist of at least one of the following.

(Pattern cured film, pattern cured film manufacturing method, semiconductor device)
The pattern cured film of the present invention can be obtained by heating the above-described resin composition of the present invention. The pattern cured film of the present invention is preferably used as a protective layer of a low-k material which is an interlayer insulating film. Examples of the low-k material include porous silica, benzocyclobutene, hydrogen silsesquioxane, polyallyl ether, and the like.

The method for producing a patterned cured film of the present invention comprises (a) a step of applying the resin composition of the present invention on a substrate and drying to form a resin film, and (b) a coating film formed in the step (a). Irradiating with actinic rays to expose to a pattern, (c) removing unexposed portions other than the exposed portions by development, and (d) heating the pattern obtained in the step (c) And forming a polyimide pattern.
First, the step (a) of applying a resin composition on a substrate and drying to form a coating film will be described. Examples of the method for applying the resin composition of the present invention on a substrate include an immersion method, a spray method, a screen printing method, and a spin coating method. Examples of the substrate include a silicon wafer, a metal substrate, and a ceramic substrate. Since the resin composition of the present invention can form a low-stress cured film, it is particularly suitable for application to a silicon wafer having a large diameter of 12 inches or more.

  After the resin composition is applied on the substrate, the solvent is removed (dried) by heating, whereby a coating film (resin film) with less adhesiveness can be formed. In addition, it is preferable that the heating temperature at the time of drying is 80-130 degreeC, and it is preferable that drying time is 30-300 second. Drying is preferably performed using an apparatus such as a hot plate.

Next, a step (b) of irradiating the coating film with an actinic ray to expose it in a pattern and a step (c) of removing an unexposed portion other than the exposed portion by development to obtain a patterned resin film will be described.
The coating film obtained by the above method is exposed in a pattern by irradiating actinic rays through a mask on which a desired pattern is drawn. Although the resin composition of the present invention is suitable for i-line exposure, ultraviolet rays, far ultraviolet rays, visible rays, electron beams, X-rays, and the like can be used as the active rays to be irradiated.

  Next, a desired pattern resin film can be obtained by dissolving and removing the unexposed portion with an appropriate developer. The developer is not particularly limited, but is a flame retardant solvent such as 1,1,1-trichloroethane, an aqueous alkali solution such as an aqueous sodium carbonate solution and an aqueous tetramethylammonium hydroxide solution, 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. After development, rinsing with a poor solvent (for example, water, ethanol, 2-propanol) or the like is performed as necessary.

  Then, the process (d) of heat-processing a pattern resin film is demonstrated. By heating the pattern obtained as described above at, for example, 80 to 400 ° C. for 5 to 300 minutes, imidation of the polyimide precursor contained in the resin composition is advanced to obtain a pattern cured film. In order to suppress the oxidative deterioration of the polyimide during heating, it is preferable to use a curing furnace that can be cured at a low oxygen concentration of 100 ppm or less, for example, an inert gas oven or a vertical diffusion furnace. Can do.

  The cured film or patterned cured film of the present invention thus obtained can be used as a surface protective layer, an interlayer insulating layer, a rewiring layer or the like of a semiconductor device.

  Examples of the semiconductor device of the present invention include Logic semiconductor devices such as MPU and memory semiconductor devices such as DRAM and NAND flash.

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

  The cured film or pattern cured film of the present invention can be used for so-called package applications such as the cover coat material, the core material for rewiring, the color material for balls such as solder, the underfill material, and the like.

  The cured film or pattern cured film of the present invention has the cured film or pattern cured film of the present invention because it has excellent adhesion to a metal layer, a sealant, and the like, as well as excellent copper migration resistance and a high stress relaxation effect. The semiconductor element is extremely excellent in reliability.

  The electronic component of the present invention is particularly limited except that it has a cover coat using the cured film or pattern cured film of the present invention, a core for rewiring, a ball collar such as solder, an underfill used in flip chips, etc. Instead, it can take various structures.

EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, this invention is not limited to these Examples.
Example 1-12, Comparative Example 1-6

(1) Synthesis of polyamic acid ester (polyimide precursor) A predetermined amount of tetracarboxylic dianhydride 1 shown in Table 1 or 2 and 2-hydroxyethyl methacrylate (2 equivalents relative to tetracarboxylic dianhydride 1) ), And a catalytic amount of 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) in N-methyl-2-pyrrolidone (4 times that of tetracarboxylic dianhydride 1 by weight). The ester solution 1 was obtained by stirring at room temperature for 48 hours.

Furthermore, if necessary, a predetermined amount of tetracarboxylic dianhydride component 2 shown in Table 1 or 2, 2-hydroxyethyl methacrylate (2 equivalents relative to tetracarboxylic dianhydride 2), and a catalytic amount Of DBU was dissolved in N-methyl-2-pyrrolidone (4 times the amount of tetracarboxylic dianhydride 2 by mass) and stirred at room temperature for 48 hours to obtain an ester solution 2.
After mixing the ester solution 1 and the ester solution 2, 2.2 equivalents of thionyl chloride was added dropwise to the total amount of tetracarboxylic dianhydrides 1 and 2 while cooling in an ice bath, followed by stirring for 1 hour. Thus, an acid chloride solution was prepared.

  Separately, a predetermined amount of diamine 1 shown in Table 1 or 2 and, if necessary, a predetermined amount of diamine 2 and pyridine (twice equivalent of thionyl chloride) were added to N-methyl-2-pyrrolidone (diamine 1 by mass ratio). And 4 times the total amount of 2) were prepared and added dropwise to the previously prepared acid chloride solution while cooling in an ice bath. After completion of the dropping, the reaction solution was dropped into distilled water, and the resulting precipitate was collected by filtration, washed several times with distilled water, and then vacuum dried to obtain a polyamic acid ester.

(2) Preparation of photosensitive resin composition Polyamic acid ester [(a) component] 100 parts by mass, tetraethylene glycol dimethacrylate 20 parts by mass, predetermined amounts of component (b) and component (c) shown in Table 1 or 2 Was stirred until it was uniformly dissolved in 150 parts by mass of N-methyl-2-pyrrolidone [component (d)], followed by pressure filtration using a 1 μm filter to obtain a resin composition.

Measurement of weight average molecular weight The weight average molecular weight of the obtained polyamic acid ester was determined in terms of standard polystyrene by gel permeation chromatography (GPC). In addition, the measurement conditions of the weight average molecular weight by GPC method are as follows.
The measurement was performed using a solution of 1 ml of a solvent [THF / DMF = 1/1 (volume ratio)] with respect to 0.5 mg of the polymer.
Measuring device: C-R4A Chromatopac manufactured by Shimadzu Corporation
Detector: L4000UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
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 of (b1-1) and (b1-3) To a 0.1 L separable flask equipped with a condenser, a stirrer, and a dropping funnel, 3-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Silicone; KBE-9007) 8.16 g (35 mmol) was added, and 2.819 g of a diluted ethanol solution of bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane (Gelest; SIB-1140.0) was reacted from the dropping funnel. The solution was added dropwise at a rate such that the reaction proceeded at a temperature of 50 ° C. or lower. After completion of dropping, the reaction solution was heated in a 60 ° oil bath for 3 hours. From the IR spectrum of the reaction solution after heating, the disappearance of the peak of the isocyanate group near 2260 cm ^-1, and a peak due to NH group near 3370cm ^-1 were observed.

  The reaction product was confirmed by thin layer column chromatography on carrier silica gel (developing solvent was hexane, color former was iodine) and disappearance of KBE-9007. From these, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane and 3-isocyanatopropyltriethoxysilane addition product (b1-1), ethanol and 3-isocyanatopropyltriethoxysilane It was confirmed that an addition product (b1-3) was obtained.

Synthesis of (b1-2) To a 0.1 L separable flask equipped with a condenser, a stirrer, and a dropping funnel, 23.311 g (100 mmol) of 3-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Silicone; KBE-9007) Into this, 3.40 g (100 mmol) of methanol was added dropwise from a dropping funnel at such a rate that the reaction proceeded when the temperature of the reaction solution was 50 ° C. or lower. After completion of dropping, the reaction solution was heated in an oil bath at 50 ° C. for 6 hours. From the IR spectrum of the reaction solution after heating, the disappearance of the peak of the isocyanate group near 2260 cm ^-1, and a peak due to NH group near 3370cm ^-1 were observed. The reaction product was confirmed by the disappearance of KBE-9007 by thin layer column chromatography on carrier silica gel (developing solvent was hexane, color former was iodine). From these, it was confirmed that an addition product of methanol and 3-isocyanatopropyltriethoxysilane (b1-2) was obtained.

Synthesis of (b1-4) To a 0.1 L separable flask equipped with a condenser, a stirrer, and a dropping funnel, 8.16 g (35 mmol) of 3-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Silicone; KBE-9007) Then, 4.524 g (35 mmol) of 2-ethylhexylamine (manufactured by Merck) was added dropwise from a dropping funnel at a rate at which the reaction proceeded at a temperature of the reaction solution of 50 ° C. or lower. After completion of the dropwise addition, the IR spectrum of the reaction solution, the disappearance of the peak of the isocyanate group near 2260 cm ^-1, and a peak due to NH group near 3370cm ^-1 were observed.
The reaction product was confirmed by the disappearance of KBE-9007 by thin layer column chromatography on carrier silica gel (developing solvent was hexane, color former was iodine). From these results, it was confirmed that an addition product (b1-4) of 2-ethylhexylamine and 3-isocyanatopropyltriethoxysilane was obtained.

Synthesis of (b1-5) To a 0.1 L separable flask equipped with a condenser, a stirrer, and a dropping funnel, 8.16 g (35 mmol) of 3-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Silicone; KBE-9007) Then, 11.56 g (35 mmol) of N-methylpyrrolidone in an amount of 2.979 g (35 mmol) of 5-aminotetrazole was added dropwise from the dropping funnel at such a rate that the reaction proceeded at a temperature of 50 ° C. or less. After completion of the dropwise addition, the IR spectrum of the reaction solution, the disappearance of the peak of the isocyanate group near 2260 cm ^-1, and a peak due to NH group near 3370cm ^-1 were observed. The reaction product was confirmed by the disappearance of KBE-9007 by thin layer column chromatography on carrier silica gel (developing solvent was hexane, color former was iodine). From these, it was confirmed that an addition product (b1-5) of 5-aminotetrazole and 3-isocyanatopropyltriethoxysilane was obtained.

Other (b1) component b1-3: triethoxysilylpropylethyl carbamate (manufactured by Gelest, SIT-8188.0)

ｂ２−２：３−グリシジルオキシプロピルトリメトキシシラン（ＫＢＭ−４０３：信越シリコーン製）

ｂ２−３：ビス（２−ヒドロキシエチル）−３−アミノプロピルトリエトキシシラン（ＳＩＢ−１１４０：Ｇｅｌｅｓｔ社製）(B2) Component b2-1: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303: Shin-Etsu Silicone)

b2-2: 3-glycidyloxypropyltrimethoxysilane (KBM-403: manufactured by Shin-Etsu Silicone)

b2-3: Bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane (SIB-1140: manufactured by Gelest)

Other alkoxysilane compounds b3: 3-isocyanatopropyltriethoxysilane (KBE-9007: manufactured by Shin-Etsu Silicone)
b4: 3-isocyanatopropyltrimethoxysilane (Y-5187: manufactured by MOMENTIVE performance materials)
b5: phenyltrimethoxysilane (KBM-103: manufactured by Shin-Etsu Silicone)

Measurement of i-Ray Transmittance A polyamic acid ester solution obtained by dissolving 100 parts by mass of the obtained polyamic acid ester in 150 parts by mass of N-methyl-2-pyrrolidone was spin-coated on a glass plate and heated at 100 ° C. on a hot plate. Then, a heat treatment was performed for 3 minutes to prepare a film having a film thickness of 20 μm, and the transmittance at 365 nm was measured. The i-line transmittance was measured by a cast film method using a visible ultraviolet spectrophotometer U-3310 manufactured by Hitachi High-Technologies Corporation and evaluated according to the following criteria.
A transmittance of 20% or more: H
Transmittance of 10% or more and less than 20%: M
Transmittance less than 10%: L

Evaluation of Photosensitive Characteristics The obtained photosensitive resin composition was applied on a 6-inch silicon wafer by a spin coating method and dried on a hot plate at 100 ° C. for 3 minutes to form a resin film having a thickness of 10 μm. The resin film is exposed through a photomask using a Canon i-line stepper FPA-3000iW by irradiating a predetermined pattern with 50-500 mJ / cm ² of i-line in increments of 50 mJ / cm ^2. It was. Also, the development time is set to twice the time until an unexposed coating film of the same thickness is immersed in cyclopentanone and completely dissolved, and the wafer after exposure is immersed in cyclopentanone and paddle developed. Thereafter, rinsing with isopropanol was performed. At this time, the minimum exposure amount at which the amount of coating film dissolved in the exposed portion was less than 10% of the initial film thickness was evaluated as sensitivity, and the minimum value of the mask dimension of the square hole-shaped opening was evaluated as resolution. The sensitivity was evaluated according to the following criteria.
300 mJ / cm ² or less: ○
More than 300 mJ / cm ² and 500 mJ / cm ² or less: Δ
Greater than 500 mJ / cm ² : ×

Evaluation of adhesion during development In the above-described evaluation of the photosensitive properties, the minimum value of peeling of the line and space pattern was measured during development, and the following criteria were evaluated.
Less than 20μm: ○
More than 20 μm and 30 μm or less:
Larger than 30 μm: ×

Measurement of Residual Stress The obtained photosensitive resin composition was applied to a 6-inch silicon wafer having a thickness of 625 μm and spin-coated so that the film thickness after curing was 10 μm. This was heat-cured at 375 ° C. for 1 hour in a nitrogen atmosphere using a vertical diffusion furnace manufactured by Koyo Lindberg to obtain a polyimide film (cured film). The residual stress of the cured polyimide film was measured at room temperature using a thin film stress measuring apparatus FLX-2320 manufactured by KLA Tencor and evaluated according to the following criteria.
Stress of 30 MPa or less: ○
Stress greater than 30 MPa and less than 35 MPa: Δ
Stress greater than 35 MPa: x

Evaluation of adhesion after curing Adhesion after curing was evaluated using a cross-cut test. The cured film was placed in a pressure cooker and treated for 200 hours under conditions of 121 ° C., 2 atm, 100% HR (PCT treatment). The adhesive strength before and after the PCT treatment was evaluated using a cross cut test.
Specifically, the cured film after treatment for 200 hours under the above PCT conditions (121 ° C./100 RH% / 2 atm) is cut into 100 grids using a cutter, and the cellophane tape is attached to the cured film. The number of peeled between the substrate and the cured film was counted and evaluated according to the following criteria.
When there is no peeling: ○
When the number of peeled is 1-50: △
When 51 or more peeled: ×

Evaluation of chemical resistance The silicon wafer with a cured film prepared for measuring the residual stress was immersed in NMP at 70 ° C. for 20 minutes, then washed with pure water to wipe off moisture adhering to the surface of the cured film. Then, it was air-dried and evaluated according to the following criteria.
The rate of change of the thickness of the cured film after air drying with respect to the initial film thickness is within ± 10%:
More than ± 10% and less than ± 20%: △
More than ± 20%: ×

The measurement results of the above evaluation are shown in Table 1 or 2.

  In Tables 1 and 2, the masses and amounts of tetracarboxylic dianhydrides 1 and 2 and diamines 1 and 2 that are raw materials for the polyimide precursor are the amounts charged. The mass part of (b) component and (c) component shows the value with respect to 100 mass parts of polyamic acid ester [(a) component].

Abbreviations in Tables 1 and 2 indicate the following compounds.
(Polyimide precursor raw material)
PMDA: pyromellitic dianhydride s-BPDA: 4,4′-biphenyltetracarboxylic dianhydride MMXDA: 9,9′-dimethyl-2,3,6,7-xanthenetetracarboxylic dianhydride ODPA: 4,4′-oxydiphthalic dianhydride TFDB: 2,2′-bis (trifluoromethyl) benzidine DMAP: 2,2′-dimethylbenzidine

(Component (c))
c1: 1,2-octanedione, 1- [4- (phenylthio) phenyl], 2- (O-benzoyloxime) (trade name “IRGACURE OXE-01” manufactured by BASF AG)
c2: Ethanone, 1- [9-ethyl-6- (2
-Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (BASF, trade name “IRGACURE OXE-02”)
c3: 4,4′-bis (diethylamino) benzophenone c4: bis [4- (2-hydroxy-2-methylpropionyl) phenyl] methane c5: bis (η ⁵ -cyclopentadienyl) bis [2,6-difluoro -3- (1H-pyr-1-yl)] phenyltitanium

  By using the component (b1) as an adhesiveness imparting agent for the photosensitive resin composition exhibiting a low stress value, the cured film has excellent adhesion to the substrate, and the component (b2) is used. Thus, the adhesion of the developed film is improved. Furthermore, it was found that by using the component (b1) and the component (b2) in combination, it has excellent adhesion after development and after curing.

  The resin composition of the present invention can be used as a protective film material or a pattern film forming material for electronic parts such as semiconductor devices.

Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will appreciate that these exemplary embodiments and / or embodiments are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of the present invention.
All the contents of the Japanese application specification that is the basis of the priority of Paris in this application are incorporated herein.

Claims (6)

A resin composition containing (a) a polyimide precursor, (b) an alkoxysilane compound, (c) a photoinitiator and (d) a solvent,
The component (a) has a structural unit represented by the following formula (1),
Wherein component (b) contains a compound represented by the compounds and the following formula represented by the following formula (4-1) (4-2),
The component (c) is a resin composition containing an oxime ester compound.

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

(In Formula (2d), X and Y are each independently 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 are each independently a hydrogen atom or a monovalent organic group, provided that R ^{3 to} R ¹⁰ are a monovalent organic group having a halogen atom and a halogen atom. is not.)

(In formula (4-1), each R ¹¹ is independently an alkyl group having 1 to 4 carbon atoms,
R ¹² is each independently a hydroxyl group or an alkyl group having 1 to 4 carbon atoms,
a is an integer of 1 to 3,
n is an integer of 1 to 6,
R ¹³ is a group of the following formula (5) or (6). )

(In Formula (5), R < ¹⁴ > is a monovalent organic group derived from a C1-C10 alkyl group or hydroxyalkylsilane.
In formula (6), R ¹⁵ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a monovalent organic group derived from aminoalkylsilane, or a heterocyclic group.
R ¹⁴ and R ¹⁵ may each have a substituent. )

(In formula (4-2), each R ¹¹ is independently an alkyl group having 1 to 4 carbon atoms,
R ¹² is each independently a hydroxyl group or an alkyl group having 1 to 4 carbon atoms,
a is an integer of 1 to 3,
n is an integer of 1 to 6,
R ¹³ is an organic group having an epoxy group or an organic group having a dihydroxyethylamino group. ) The resin composition according to claim 1, wherein the component (c) is a compound represented by the following formula (7).

(In formula (7), R ^{16 to} R ²² are each independently a hydrogen atom or a monovalent group.) The resin composition according to claim 1 or 2 , wherein the component (a) further has a structural unit represented by the following formula (9).

(In formula (9), D is a tetravalent organic group represented by the following formula (10),
B, R ¹ and R ² are the same as those in the formula (1). )

(In Formula (10), Z is an oxygen atom or a sulfur atom.) (A) applying the resin composition according to any one of claims 1 to 3 on a substrate and drying to form a coating film;
(B) a step of irradiating the coating film formed in the step (a) with an actinic ray to expose it in a pattern;
(C) removing unexposed portions other than the exposed portions by development;
(D) A process for producing a cured pattern film, comprising a step of heat-treating the pattern obtained in the step (c) to form a polyimide pattern. The cured film which hardened the resin composition in any one of Claims 1-3 . An electronic component having the cured film according to claim 5 as an interlayer insulating film layer and / or a surface protective film layer.

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