KR20160110496A - Photosensitive resin composition, cured-relief-pattern production method, and semiconductor device - Google Patents

Abstract

The photosensitive resin composition comprises (A) a polyimide precursor such as polyamide acid, polyamide acid ester, polyamide acid salt, polyamide acid amide, polyhydroxyamide which may be a polyoxazole precursor, polyaminoamide, polyamide, At least one resin selected from the group consisting of polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, polybenzothiazole, and phenol resin;
(B) a photosensitizer, and (C) a polyfunctional (meth) acrylate and a low molecular weight imide compound having a molecular weight of less than 1,000.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a method of producing a cured relief pattern, and a semiconductor device,

The present invention relates to a photosensitive resin composition used for forming a relief pattern, for example, an insulating material for electronic parts, a passivation film for a semiconductor device, a buffer coat film and an interlayer insulating film, a method for producing a cured relief pattern using the same, A semiconductor device having a relief pattern, and a resin film excellent in adhesion to a polybenzoxazole resin.

BACKGROUND ART Conventionally, a resin such as polyimide having excellent heat resistance, electrical characteristics, and mechanical characteristics has been used as an insulating material for electronic parts, a passivation film, a surface protective film, an interlayer insulating film, and the like of a semiconductor device. Among resins such as polyimide, a resin provided in the form of a photosensitive polyimide precursor easily forms a heat-resistant relief pattern film by heat imidation treatment by coating, exposure, development and curing of the precursor thereof can do. The photosensitive polyimide precursor has a feature that it can significantly shorten the process time as compared with the conventional non-photosensitive polyimide.

On the other hand, in recent years, the mounting method of the semiconductor device on the printed wiring board is also changing from the viewpoints of improvement of the integration degree and function, and reduction of the chip size. It has been found that a coating of a resin such as polyimide such as BGA (Ball Grip Door Ray) and CSP (Chip Size Packaging) which can be mounted with a higher density from a conventional metal pin and a soldering method using lead- Is used as a contact structure. When such a bump structure is formed, the coating film is required to have high heat resistance and chemical resistance. There is disclosed a method for improving the heat resistance of a polyimide coating or a polybenzoxazole coating by adding a heat crosslinking agent to a composition comprising a polyimide precursor or a polybenzoxazole precursor (see Patent Document 1).

Japanese Patent Application Laid-Open No. 2003-287889

In the rewiring process of the semiconductor device, since the process of forming the interlayer insulating film is separately performed by the maker of the major definition maker and the maker of the later process, the polybenzoxazole film formed in the previous process is subjected to a post- The number of coatings of the coating layer is increasing. However, in the conventional photosensitive resin composition, when an additional coating film is formed on the polybenzoxazole coating film, there is a problem that peeling occurs after development / curing because of insufficient adhesion. Adhesion auxiliary agents for improving adhesion of resins to Si substrates and Cu substrates have been heretofore known, but there has been a problem that the use of an adhesion aid agent deteriorates the resolution or heat resistance of the relief pattern.

Further, when forming the seed layer of the metal re-wiring layer, it is necessary to sputter the metal on the surface of the resin without gaps. For this purpose, it is preferable that the opening portion of the photosensitive resin pattern be a net tapered shape whose side surface is gentler than the vertical surface at the time of completion of patterning, preferably a taper angle of 80 DEG or less. However, Even when the composition is used, it has been difficult to make the side surface of the opening portion into a net taper shape at the end of the patterning.

Therefore, a problem to be solved by the present invention is to provide a cured film which is excellent in adhesion to a polybenzoxazole resin, a Si substrate and a Cu substrate, has high resolution and heat resistance, and further has a side surface of the opening portion in a tapered shape A method for producing a cured relief pattern using the photosensitive resin composition, a semiconductor device having the cured relief pattern, and a resin film excellent in adhesiveness to a polybenzoxazole resin have a glass transition temperature of 250 占 폚 or less And a laminated body laminated on a resin substrate.

The present inventors have found that a photosensitive resin composition obtained by specifying either the resin structure, the kind of the initiator, or the coupler is excellent in adhesiveness to polybenzoxazole resin, Si substrate and Cu substrate, has high resolution and heat resistance, And a resin film having a specific crosslinking density and a specific 5% weight reduction temperature, which contains a specific resin and which has a specific crosslinking density and a specific 5% weight reduction temperature, is provided with a polybenzoxazole Can be laminated on a resin substrate having a glass transition temperature of 250 占 폚 or less, in addition to excellent adhesion to a resin. Thus, the present invention has been accomplished. That is, the present invention is as follows.

[One]

The following ingredients:

(A) a polyimide precursor which is a polyamide acid, a polyamide acid ester, a polyamide acid salt, a polyamide acid amide, a polyhydroxyamide which may be a polyoxazole precursor, a polyaminoamide, a polyamide, a polyamideimide, At least one resin selected from the group consisting of polybenzoxazole, polybenzimidazole, polybenzothiazole, and phenol resin;

(B) a photosensitizer; and

(C) at least one member selected from the group consisting of polyfunctional (meth) acrylates and low molecular weight imide compounds having a molecular weight of less than 1000;

.

[2]

Wherein the component (A) is at least one selected from the group consisting of polyamide acid, polyamide acid ester, polyamide acid salt, polyamide acid amide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, Wherein the resin is at least one resin selected from the group consisting of polybenzothiazole.

[3]

The photosensitive resin composition according to [1] or [2], wherein the component (C) is a low molecular weight imide compound having a molecular weight of less than 1,000.

[4]

Wherein the component (A) is a compound represented by the following general formula (A1):

[Chemical Formula 1]

{Wherein, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, l is an integer of 2 ~ 150, R ₁ and R ₂ are, each independently, a hydrogen atom, or a radical Is a polymerizable monovalent organic group. Provided that both of R ₁ and R ₂ are not hydrogen atoms at the same time.

Is a polyimide precursor represented by the following formula

Wherein the component (C) is a compound represented by the following general formula (C1):

(2)

Wherein R ₃ is a single bond, a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₄ and R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, An aryl group, an alkoxy group or a halogen atom, and m is an integer of 1 or more.

The photosensitive resin composition according to any one of [1] to [3], wherein the photosensitive resin composition contains maleimide represented by the following formula (1).

[5]

Wherein the component (A) is a compound represented by the following general formula (A2):

(3)

Wherein, in the formula, X ₂ is a tetravalent organic group, Y ² is a divalent organic group, n is an integer of 2 to 150, R ₆ and R ₇ are each independently a hydrogen atom, Formula (A3):

[Chemical Formula 4]

(Wherein R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer of 2 to 10)

, Or a saturated aliphatic group having 1 to 4 carbon atoms. Provided that both of R < ₆ > and R < ₇ > are not simultaneously hydrogen atoms.

The photosensitive resin composition according to any one of [1] to [4], which is a polyimide precursor represented by the following general formula (1).

[6]

Wherein the component (C) is a compound represented by the following general formula (C2):

[Chemical Formula 5]

Wherein R ₁₁ is a single bond, a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₁₂ and R ₁₃ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, An aryl group, an alkoxy group or a halogen atom, and q is an integer of 2 to 4.

The photosensitive resin composition according to any one of [1] to [5], wherein the photosensitive resin composition contains maleimide.

[7]

The photosensitive resin composition according to any one of [1] to [6], wherein the component (B) is a oxime-based photopolymerization initiator.

[8]

Wherein the component (B) comprises the following components (B1) and (B2):

An oxime ester compound in which the i-line absorbance of the 0.001 wt% solution of (B1) is 0.15 to 0.5, and the g-line absorbance and the h-ray absorbance of the 0.001 wt% solution are 0.2 or less;

(B2) an oxime ester compound having an i-line absorbance of not more than 0.1 and a g line absorbance or a h line absorbance of not less than 0.05 in a 0.001 wt% solution;

The photosensitive resin composition according to any one of [1] to [7], wherein the photosensitive resin composition contains at least one kind selected from the group consisting of

[9]

The photosensitive resin composition according to [8], wherein the i-line absorbance of the 0.001 wt% solution of the component (B1) is 0.15 to 0.35.

[10]

Wherein the component (B1) is a compound represented by the following general formula (B11) and (B12):

[Chemical Formula 6]

Wherein R ₁₄ is a fluorine-containing alkyl group having ₁ to ₁₀ carbon atoms, and R ₁₅ , R ₁₆ and R ₁₇ are each independently a C ₁ to C ₂₀ alkyl group, a C ₃ to C ₂₀ cycloalkyl group, A C ₆ to C ₂₀ aryl group, or a C ₁ to C ₂₀ alkoxy group, and r is an integer of 0 to 5.

(7)

{Wherein, R ₁₈ is a divalent organic group of _{C 1 ~ C 30, R 19} ~ R 26 are, each independently, C ₁ ~ C ₂₀ alkyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ An aryl group of C ₂₀ , or an alkoxy group of C ₁ to C ₂₀ , and s is an integer of 0 to 3.

The photosensitive resin composition according to [8] or [9], wherein the photosensitive resin composition contains at least one member selected from the group consisting of oxime ester compounds represented by the following formulas.

[11]

In addition to the above components (A) to (C)

(D) a compound represented by the following general formula (D1):

[Chemical Formula 8]

Wherein R ₂₇ and R ₂₈ are C ₁ -C ₄ alkyl groups, R ₂₉ is a divalent organic group of C ₁ to C ₆ , and R ₃₀ is selected from the group consisting of nitrogen, oxygen, and sulfur a C organic group of ₁ ~ C ₂₀ binding to the carbonyl group by an atom, t is an integer selected from 1, 2, and 3, u is an integer selected from 0, 1, and 2, and t and u , t + u = 3 are satisfied.

The photosensitive resin composition according to any one of [1] to [10], which contains a silicon-containing compound represented by the following general formula (1).

[12]

(D2) shown below in addition to the silicon-containing compound represented by the formula (D1) as the component (D)

[Chemical Formula 9]

Wherein R ₃₁ and R ₃₂ are a C ₁ -C ₄ alkyl group, R ₃₃ is a divalent organic group of C ₁ to C ₆ , v is an integer selected from 1, 2, and 3, and w is 0, 1, and 2, and v and w satisfy the relationship v + w = 3.

The photosensitive resin composition according to [11], further comprising a silicon-containing compound represented by the following formula

[13]

In addition to the above components (A) to (C)

(E) represented by the following general formula (E1):

[Chemical formula 10]

Wherein R ₃₄ is a C ₁ to C ₂₀ organic group or a silicon-containing organic group and R ₃₅ is a C ₁ to C ₂₀ group bonded with a thiocarbonyl group by an atom selected from the group consisting of nitrogen, oxygen, .

The photosensitive resin composition according to any one of [1] to [10], wherein the photosensitive resin composition contains a sulfur-containing compound represented by the following general formula (1).

[14]

With respect to 100 parts by mass of the component (A)

0.1 to 20 parts by mass of the component (B)

1 to 40 parts by mass of the component (C);

The photosensitive resin composition according to any one of [1] to [10], further comprising:

[15]

With respect to 100 parts by mass of the component (A)

0.1 to 20 parts by mass of the component (B)

10 to 35 parts by mass of the component (C);

The photosensitive resin composition according to any one of [1] to [10], further comprising:

[16]

With respect to 100 parts by mass of the component (A)

0.1 to 20 parts by mass of the component (B);

1 to 40 parts by mass of the component (C)

0.1 to 20 parts by mass of the component (D);

[11] The photosensitive resin composition according to [11] or [12]

[17]

With respect to 100 parts by mass of the component (A)

0.1 to 20 parts by mass of the component (B);

10 to 35 parts by mass of the component (C)

0.1 to 20 parts by mass of the component (D);

[11] The photosensitive resin composition according to [11] or [12]

[18]

With respect to 100 parts by mass of the component (A)

0.1 to 20 parts by mass of the component (B);

1 to 40 parts by mass of the component (C)

0.1 to 20 parts by mass of the component (E);

The photosensitive resin composition according to [13], further comprising:

[19]

With respect to 100 parts by mass of the component (A)

0.1 to 20 parts by mass of the component (B);

10 to 35 parts by mass of the component (C)

0.1 to 20 parts by mass of the component (E);

The photosensitive resin composition according to [13], further comprising:

[20]

The following ingredients:

(AX) photosensitive polyimide precursor;

The following components (B1) and (B2)

(B1) an oxime ester compound in which the i-line absorbance of the 0.001 wt% solution is from 0.15 to 0.5, and the g-line absorbance and h-line absorbance of the 0.001 wt% solution are 0.2 or less, and

(B2) 0.001 wt% solution having an i-line absorbance of 0.1 or less and a g line absorbance or h line absorbance of 0.001 wt% solution of 0.05 or more,

At least one member selected from the group consisting of

And a photosensitive resin composition.

[21]

Wherein the component (AX) is a compound represented by the following general formula (A2):

(11)

Wherein, in the formula, X ₂ is a tetravalent organic group, Y ² is a divalent organic group, n is an integer of 2 to 150, R ₆ and R ₇ are each independently a hydrogen atom, Formula (A3):

[Chemical Formula 12]

(Wherein R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer of 2 to 10)

, Or a saturated aliphatic group having 1 to 4 carbon atoms. Provided that both of R < ₆ > and R < ₇ > are not simultaneously hydrogen atoms.

Is a polyimide precursor represented by the following general formula (20).

[22]

The photosensitive resin composition according to [20] or [21], wherein the i-line absorbance of the 0.001 wt% solution of the component (B1) is 0.15 to 0.35.

[23]

Wherein the component (B1) is a compound represented by the following general formula (B11) and (B12):

[Chemical Formula 13]

Wherein R ₁₄ is a fluorine-containing alkyl group having ₁ to ₁₀ carbon atoms, and R ₁₅ , R ₁₆ and R ₁₇ are each independently a C ₁ to C ₂₀ alkyl group, a C ₃ to C ₂₀ cycloalkyl group, A C ₆ to C ₂₀ aryl group, or a C ₁ to C ₂₀ alkoxy group, and r is an integer of 0 to 5.

[Chemical Formula 14]

{Wherein, R ₁₈ is a divalent organic group of _{C 1 ~ C 30, R 19} ~ R 26 are, each independently, C ₁ ~ C ₂₀ alkyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ An aryl group of C ₂₀ , or an alkoxy group of C ₁ to C ₂₀ , and s is an integer of 0 to 3.

The photosensitive resin composition according to any one of [20] to [22], wherein the photosensitive resin composition contains at least one member selected from the group consisting of oxime ester compounds represented by the following formulas:

[24]

The photosensitive resin composition according to any one of (20) to (23), wherein the total content of the component (B1) and the component (B2) relative to 100 parts by mass of the component (AX) is 0.1 to 10 parts by mass.

[25]

The photosensitive resin composition according to any one of (20) to (24), wherein the total content of the component (B1) and the component (B2) relative to 100 parts by mass of the component (AX) is 0.5 to 5 parts by mass.

[26]

The following ingredients:

(AY) polyimide precursor; and

(D) a compound represented by the following general formula (D1):

[Chemical Formula 15]

Wherein R ₂₇ and R ₂₈ are C ₁ -C ₄ alkyl groups, R ₂₉ is a divalent organic group of C ₁ to C ₆ , and R ₃₀ is selected from the group consisting of nitrogen, oxygen, and sulfur a C organic group of ₁ ~ C ₂₀ binding to the carbonyl group by an atom, t is an integer selected from 1, 2, and 3, u is an integer selected from 0, 1, and 2, and t and u , t + u = 3 are satisfied.

A silicon-containing compound represented by the formula

. ≪ / RTI >

[27]

(D2) shown below in addition to the silicon-containing compound represented by the formula (D1) as the component (D)

[Chemical Formula 16]

Wherein R ₃₁ and R ₃₂ are a C ₁ -C ₄ alkyl group, R ₃₃ is a divalent organic group of C ₁ to C ₆ , v is an integer selected from 1, 2, and 3, and w is 0, 1, and 2, and v and w satisfy the relationship v + w = 3.

The resin composition according to [26], further comprising a silicon-containing compound represented by the following formula

[28]

The following ingredients:

(AY) polyimide precursor; and

(E) represented by the following general formula (E1):

[Chemical Formula 17]

Wherein R ₃₄ is a C ₁ -C ₂₀ organic group or a silicon-containing organic group and R ₃₅ is a C ₁ -C ₂₀ alkyl group which is bonded to a thiocarbonyl group by an atom selected from the group consisting of nitrogen, oxygen and sulfur .

A sulfur-containing compound represented by the following formula

. ≪ / RTI >

[29]

Wherein the component (AY) is a compound represented by the following general formula (A2):

[Chemical Formula 18]

Wherein, in the formula, X ₂ is a tetravalent organic group, Y ² is a divalent organic group, n is an integer of 2 to 150, R ₆ and R ₇ are each independently a hydrogen atom, Formula (A3):

[Chemical Formula 19]

(Wherein R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer of 2 to 10)

, Or a saturated aliphatic group having 1 to 4 carbon atoms. Provided that both of R < ₆ > and R < ₇ > are not simultaneously hydrogen atoms.

Is a polyimide precursor represented by the following general formula (26).

[30]

With respect to 100 parts by mass of the component (AY)

0.1 to 20 parts by mass of the component (D1)

0.1 to 20 parts by mass of the component (D2);

[27] The resin composition according to [27],

[31]

The resin composition according to (28) or (29), which comprises 0.1 to 20 parts by mass of the component (E), based on 100 parts by mass of the component (AY).

[32]

The resin composition according to any one of (26) to (31), further comprising (B) a photosensitizer.

[33]

The following:

(1) A process for producing a photosensitive resin composition, comprising the steps of: applying the photosensitive resin composition described in any one of [1] to [25] or the resin composition described in [32] on a substrate to form a photosensitive resin layer on the substrate;

(2) a step of exposing the photosensitive resin layer,

(3) developing the exposed photosensitive resin layer to form a relief pattern,

(4) a step of providing a relief pattern to a heat treatment to form a cured relief pattern

≪ / RTI >

[34]

A semiconductor device comprising a cured relief pattern obtained by the manufacturing method according to [33].

[35]

The following ingredients:

(A) a polyimide precursor which is a polyamide acid, a polyamide acid ester, a polyamide acid salt, a polyamide acid amide, a polyhydroxyamide which may be a polyoxazole precursor, a polyaminoamide, a polyamide, a polyamideimide, At least one resin selected from the group consisting of polybenzoxazole, polybenzoxazole, polybenzimidazole, polybenzothiazole, and phenol resin,

Lt; / RTI >

The crosslinking density is 1.0 × 10 ^-4 mol / cm 3 or more and 3.0 × 10 ^-3 mol / cm 3 or less,

5% weight reduction temperature is 250 占 폚 or higher and 400 占 폚 or lower,

Resin film.

[36]

The resin film according to [35], wherein the cross-linking density is 3.0 × 10 ^-4 mol / cm 3 or more and 2.0 × 10 ^-3 mol / cm 3 or less.

[37]

Wherein the component (A) is at least one selected from the group consisting of polyamide acid, polyamide acid ester, polyamide acid salt, polyamide acid amide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, The resin film described in [35] or [36], which is at least one resin selected from the group consisting of polybenzothiazole.

[38]

A laminate in which the resin film described in any one of [35] to [37] is laminated on a resin substrate having a glass transition temperature of 200 ° C or less.

[39]

A laminate in which the resin film described in any one of [35] to [37] is laminated on a resin substrate having a glass transition temperature of 250 ° C or less.

According to the present invention, there is provided a photosensitive resin composition for producing a cured film excellent in adhesiveness to a polybenzoxazole resin, a Si substrate and a Cu substrate, high in resolution and heat resistance, A method for producing a cured relief pattern using a photosensitive resin composition, a semiconductor device having the cured relief pattern, and a resin film excellent in adhesiveness to a polybenzoxazole resin, and a resin film thereof having a glass transition temperature of 250 DEG C or less And the laminated body is laminated on the substrate.

1A is a schematic view showing one step of a taper angle evaluation method.
Fig. 1B is a schematic view showing a step of a taper angle evaluation method. Fig.
Fig. 1C is a schematic view showing a step of a taper angle evaluation method. Fig.
1D is a schematic view showing one step of a taper angle evaluation method.
1E is a schematic view showing one step of a taper angle evaluation method.

The present invention will be described in detail below. Throughout this specification, the structures represented by the same symbols in the general formulas may be the same or different from each other when a plurality of structures exist in the molecule.

<Resin composition>

(A) a polyimide precursor which is a polyamide acid, a polyamide acid ester, a polyamide acid salt, a polyamide acid amide, a polyhydroxyamide which may be a polyoxazole precursor, a polyaminoamide, a polyamide, a polyamideimide, At least one resin selected from the group consisting of polybenzoxazole, polybenzimidazole, polybenzothiazole, and phenol resin;

(B) a photosensitizer; and

(C) at least one member selected from the group consisting of polyfunctional (meth) acrylates and low molecular weight imide compounds having a molecular weight of less than 1000;

Will be described.

(A) Component

The component (A) used in the present composition is a polyimide precursor such as polyamide acid, polyamide acid ester, polyamide acid salt, polyamide acid amide, polyhydroxyamide which may be a polyoxazole precursor, polyaminoamide, At least one resin selected from the group consisting of polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, polybenzothiazole, and phenol resin. Among them, from the viewpoint of adhesion with the polybenzoxazole resin, polyamide acid, polyamide acid ester, polyamide acid salt, polyamide acid amide, polyamide, polyamideimide, polyimide, polybenzoxazole, At least one resin selected from the group consisting of imidazole and polybenzothiazole is preferable.

The weight average molecular weight of these resins is preferably 1,000 or more, more preferably 5,000 or more, in terms of polystyrene by gel permeation chromatography from the viewpoints of heat resistance after heat treatment and mechanical properties. The upper limit of the weight average molecular weight is preferably 100,000 or less.

The resin of the component (A) is preferably a photosensitive resin in order to form a relief pattern with the resin composition. The photosensitive resin is a resin that forms a photosensitive resin composition when used together with a photosensitive agent (B) to be described later and causes a phenomenon due to dissolution or non-dissolution in the subsequent developing step.

Examples of the photosensitive resin include polyimide precursors such as polyamide acid, polyamide acid ester, polyamide acid salt, polyamide acid amide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, Among the sols, a polyimide precursor, a polyamide, and / or a polyimide are preferably used from the viewpoint that the heat-treated resin is excellent in heat resistance and mechanical properties. These photosensitive resins can be selected in accordance with the intended use from the standpoint of which photosensitive resin composition, negative or positive photosensitive resin composition, is to be prepared together with the photosensitive resin (B) to be described later.

[Polyimide precursor]

In the resin composition of the present invention, one of the resin (A), the photosensitive polyimide precursor (AX) and the polyimide precursor (AY) is preferably represented by the following general formula (A1)

[Chemical Formula 20]

{Wherein, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, l is an integer of 2 ~ 150, R ₁ and R ₂ are, each independently, a hydrogen atom, or a radical Is a polymerizable monovalent organic group. Provided that both of R ₁ and R ₂ are not hydrogen atoms at the same time.

, More preferably a polyamide having a structure represented by the following general formula (A2):

[Chemical Formula 21]

Wherein, in the formula, X ₂ is a tetravalent organic group, Y ² is a divalent organic group, n is an integer of 2 to 150, R ₆ and R ₇ are each independently a hydrogen atom, Formula (A3):

[Chemical Formula 22]

(Wherein R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer of 2 to 10)

, Or a saturated aliphatic group having 1 to 4 carbon atoms. Provided that both of R &lt; ₆ &gt; and R &lt; ₇ &gt; are not simultaneously hydrogen atoms.

. &Lt; / RTI &gt;

The resin (A), the photosensitive polyimide precursor (AX), or the polyimide precursor (AY) is converted into polyimide by heating (for example, 180 ° C or more).

In the general formula (A2), the tetravalent organic group represented by X ₂ is preferably an organic group having 6 to 40 carbon atoms from the viewpoints of heat resistance and photosensitive properties, more preferably a -COOR ₆ group and a -COOR ₇ group -CONH- group is an aromatic group or an alicyclic aliphatic group in ortho position with respect to each other. X ₂ is more preferably a tetravalent organic group represented by the following formula:

(23)

, But the present invention is not limited to these structures. The structure of X ₂ may be one species or a combination of two or more species.

In the general formula (A2), the divalent organic group represented by Y ² is preferably an aromatic group having 6 to 40 carbon atoms from the viewpoints of heat resistance and photosensitive properties, and includes, for example,

&Lt; EMI ID =

(25)

(Wherein A represents a methyl group (-CH ₃ ), an ethyl group (-C ₂ H ₅ ), a propyl group (-C ₃ H ₇ ) or a butyl group (-C ₄ H ₉ ).

, But the present invention is not limited to these structures. The structure of Y ² may be one species or a combination of two or more species.

R R ₈ is preferably a hydrogen atom or a methyl group, and, R ₉ and R ₁₀ in the general formula (A3), for ₆ and R ₇ are preferably hydrogen atoms in terms of the photosensitivity. Also, p is an integer of preferably 2 or more and 10 or less, and more preferably 2 or more and 4 or less, from the viewpoint of photosensitive characteristics.

Examples of the method of imparting photosensitivity to the photosensitive resin composition when a polyimide precursor is used as the resin of the component (A) and when the photosensitive polyimide precursor (AX) or the (AY) polyimide precursor is used, And an ion-binding type. The former is a method of introducing a compound having a photopolymerizable group, that is, a compound having an olefinic double bond, into the side chain of the polyimide precursor by ester bonding, and the latter is a method in which a carboxyl group of the polyimide precursor and (meth) acrylic compound Is bonded through an ionic bond to give a photopolymerizable group.

[Method for preparing polyimide precursor]

The ester bond type polyimide precursor is obtained by first reacting a tetracarboxylic acid dianhydride containing the above tetravalent organic group X ₂ with an alcohol having a photopolymerizable unsaturated double bond and optionally a saturated aliphatic alcohol, (Hereinafter, also referred to as an acid / ester compound), and then subjecting the resultant to diamide-containing diamines including the bivalent organic group Y ₂ to amide polycondensation.

(Preparation of an acid / ester form)

Examples of the tetracarboxylic acid dianhydride having a tetravalent organic group X ₂ , which is preferably used for preparing an ester bond-type polyimide precursor, include pyromellitic anhydride, diphenyl ether-3,3 ' , 4,4'-tetracarboxylic acid dianhydride, benzophenone-3,3 ', 4,4'-tetracarboxylic acid dianhydride, biphenyl-3,3', 4,4'-tetracarboxylic acid Dianhydride, diphenylsulfone-3,3 ', 4,4'-tetracarboxylic acid dianhydride, diphenylmethane-3,3', 4,4'-tetracarboxylic acid dianhydride, 2,2-bis (3,4-anhydrophthalic acid) propane, and 2,2-bis (3,4-anhydrophthalic acid) -1,1,1,3,3,3-hexafluoropropane. It is not. These may be used alone or as a mixture of two or more.

Examples of alcohols having a photopolymerizable unsaturated double bond which are preferably used for preparing an ester bond type polyimide precursor include 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3- Propyl alcohol, 2-acrylamide ethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy- Hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3- 2-methacryloyloxyethyl alcohol, 2-methacryloyloxyethyl alcohol, 2-hydroxy-3-methoxypropyl methacrylate, 2-methacryloyloxyethyl alcohol, -Hydroxy-3-butoxypropyl methacrylate, 2- Hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy- Hexyloxypropyl methacrylate, and the like.

As the saturated aliphatic alcohol having 1 to 4 carbon atoms, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, etc. may be mixed with an alcohol having a photopolymerizable unsaturated double bond.

The above-described preferable tetracarboxylic acid dianhydride and the above-described preferred alcohols are stirred in a suitable reaction solvent at 20 to 50 ° C for 4 to 10 hours in the presence of a basic catalyst such as pyridine and dissolved , The esterification reaction of the acid anhydride proceeds to obtain a desired acid / ester product.

The reaction solvent is preferably an acid / ester compound and a solvent which completely dissolves the polyimide precursor which is an amide polycondensation product of the compound and the diamine component. Examples thereof include N-methyl-2-pyrrolidone, N, N -Dimethyl acetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea and? -Butyrolactone.

Examples of the other reaction solvent include ketones, esters, lactones, ethers, halogenated hydrocarbons and hydrocarbons, and examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate , Ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o- , Hexane, heptane, benzene, toluene, xylene, and the like. These may be used alone or in a mixture of two or more as necessary.

(Preparation of polyimide precursor)

To a solution of an acid / ester (typically a solution in a reaction solvent) under ice-cooling, a suitable dehydrating condensing agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy- Dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'-disuccinimidyl carbonate, and the like are mixed and mixed to prepare an acid / Conversion to polyacid anhydride. Thereafter, a desired photosensitive resin can be obtained by dropping a solution or dispersion obtained by dissolving or dispersing a diamine containing a desired bivalent organic group Y ₁ in a separate solvent into a polyacid anhydride and then carrying out amide polycondensation .

Preferable diamines including divalent organic group Y ₁ include, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether , 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'- Diaminodiphenylsulfone, 4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl , 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenyl Methane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3- Benzene, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- Bis (4-aminophenoxy) biphenyl, Bis (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 9,10- Bis [4- (4-aminophenoxy) phenyl) propane, 2,2-bis [4- (3-aminopropyldimethylsilyl) benzene, ortho-tolylidinesulfone, and 9,9-bis (4-aminophenyl) fluorene; the hydrogen atoms on the benzene ring of these diamines A part of which is substituted with a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, a halogen or the like such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- , 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'- Methane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof. It is not.

When the polyimide precursor is used as the resin of the component (A) and the component (AX) is used as the resin of the component (A) in order to improve the adhesion between the photosensitive resin layer formed on the substrate and various substrates by applying the photosensitive resin composition of the present invention onto the substrate, (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (3-aminopropyl) tetraphenyldisiloxane and the like can be used in the case of preparing a photosensitive polyimide precursor or (AY) polyimide precursor And diaminosiloxanes may be copolymerized.

After completion of the amide polycondensation reaction, the absorbent by-product of the dehydrating condensing agent coexisting in the reaction liquid is separated by filtration if necessary, and then a poor solvent such as water, an aliphatic lower alcohol or a mixture thereof is added to the obtained polymer component And the polymer component is precipitated, and further the polymer is purified by repeating redissolution, reprecipitation precipitation and the like, and vacuum drying is carried out to isolate the desired polyimide precursor. In order to improve the degree of purification, the ionic impurities may be removed through a solution of the anion and / or the cation exchange resin in a column filled with a suitable organic solvent by swelling.

The weight average molecular weight of the ester-bonded polyimide precursor is preferably 8,000 to 150,000, more preferably 9,000 to 50,000 in terms of polystyrene by gel permeation chromatography. When the weight average molecular weight is 8,000 or more, the mechanical properties are good. When the weight average molecular weight is 150,000 or less, the dispersibility to the developer is good and the relief pattern has good resolution. As a developing solvent for gel permeation chromatography, tetrahydrofuran and / or N-methyl-2-pyrrolidone are recommended. The molecular weight is obtained from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is preferable to select STANDARD SM-105, an organic solvent-based standard sample manufactured by Showa Denko KK.

(B) Photosensitizer

As the photosensitizer (B), a compound conventionally used as a photo polymerization initiator for UV curing can be arbitrarily selected. Examples of the compound which can be preferably used as the (B) photosensitive agent include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone and fluorenone; Acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone and 1-hydroxycyclohexylphenylketone; thioxanthone, 2-methylthioxanthone, Thioxanthone derivatives such as propyl thioxanthone and diethyl thioxanthone; benzyl derivatives such as benzyl, benzyldimethyl ketal and benzyl-? -Methoxyethyl acetal; benzoin such as benzoin and methyl benzoate; 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl- Phenyl-1,2-propanedione-2- (o-benzoyl) oxime, 1,3-diphenylpropanetrion -2- (o-ethoxycar N-arylglycines such as N-phenylglycine, peroxides such as benzoyl perchloride, aromatic hydrocarbons such as benzoyl peroxide, aromatic hydrocarbons such as benzoyl peroxide, Imidazoles, and the like, but the present invention is not limited thereto. One of these may be used, or a mixture of two or more may be used. Of these, oximes are more preferable from the viewpoint of light sensitivity.

(B) oximes which are used as photosensitizers include the following components (B1) and (B2):

(B1), an oxime ester compound having a g-ray absorbance and a h-ray absorbance of 0.2 or less and an i-line absorbance of 0.15 to 0.5, and

An oxime ester compound having a g-ray absorbance or a h-ray absorbance of 0.05 or more and an i-line absorbance of 0.1 or less with respect to 0.001 wt% of the (B2) solution;

At least one kind selected from the group consisting of

The absorbance of the oxime ester compound can be measured by dissolving the compound in N-methylpyrrolidone at a concentration of 0.001 wt%, using a 1 cm quartz cell and a conventional spectrophotometer.

(Trade name, manufactured by BASF), ADEKA OPTIMER NCI831 (trade name, manufactured by ADEKA), TR-PBG326 (trade name, manufactured by Sangho Power Electronics New Material Co., Ltd.), and the like, HTPI426 (trade name, manufactured by Heraeus Co., Ltd.), HTPI428 (trade name, manufactured by Heraeus Co., Ltd.), and mixtures thereof.

When a compound having an i-line absorbance of 0.001 wt% or less as the component (B1) is smaller than 0.15, it is necessary to add a large amount of initiator for curing because of insufficient absorbance. In this case, since the surface hardness is increased and the surface of the coating film is hardly influenced by the oxygen inhibition, the openings after exposure and development do not become net tapered. When the i-line absorbance exceeds 0.5, or when at least one of the g-line absorbance and the h-line absorbance exceeds 0.2, the absorbance is too high and the surface hardening tends to proceed. .

More preferred component (B1) is an oxime ester compound having an i-line absorbance of 0.15 to 0.35 in 0.001 wt% solution. More preferred component (B1) is a compound represented by general formula (B11)

(26)

Wherein R ₁₄ is a fluorine-containing alkyl group having ₁ to ₁₀ carbon atoms, and R ₁₅ , R ₁₆ and R ₁₇ are each independently a C ₁ to C ₂₀ alkyl group, a C ₃ to C ₂₀ cycloalkyl group, A C ₆ to C ₂₀ aryl group, or a C ₁ to C ₂₀ alkoxy group, and r is an integer of 0 to 5.

(27)

{Wherein, R ₁₈ is a divalent organic group of _{C 1 ~ C 30, R 19} ~ R 26 are, each independently, C ₁ ~ C ₂₀ alkyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ An aryl group of C ₂₀ , or an alkoxy group of C ₁ to C ₂₀ , and s is an integer of 0 to 3.

And an oxime ester compound represented by the following general formula (1).

In the photosensitive resin composition of the present invention, the oxime ester compound of component (B2) also functions as a photopolymerization initiator.

The absorbance of the oxime ester compound of the component (B2) can be measured in the same manner as in the case of the oxime ester compound of the component (B1).

As a preferable compound as the component (B2), for example, TR-PBG340 (trade name, manufactured by Sangju Strong Electronics New Material Co., Ltd.) can be mentioned.

When a compound having a g-ray absorbance of 0.001 wt% as the component (B2) and a h-ray absorbance of less than 0.05 is used, a large amount of initiator needs to be added for curing because of insufficient absorbance. In this case, since the surface hardness is increased and the surface of the coating film is hardly influenced by the oxygen inhibition, the openings after exposure and development do not become net tapered. Even when the i-line absorbance exceeds 0.1, the absorbance is too high and the surface hardening tends to proceed, so that the openings after exposure and development do not become net tapered.

The total amount of the component (B1) and the component (B2) is preferably in the range of 0.1 to 20 parts by mass relative to 100 parts by mass of the resin (A), the photosensitive polyimide precursor (AX) More preferably 0.5 to 5 parts by mass. When the total amount of the component (B1) and the component (B2) is 0.1 parts by mass or more based on 100 parts by mass of the resin (A), the photosensitive polyimide precursor (AX) or the polyimide precursor (AY) , And when it is 20 parts by mass or less, the net taper property is excellent.

(C) at least one member selected from the group consisting of polyfunctional (meth) acrylates and low molecular weight imide compounds having a molecular weight of less than 1000

(C) is at least one member selected from the group consisting of a polyfunctional (meth) acrylate and a low molecular weight imide compound having a molecular weight of less than 1,000. "(Meth) acrylate" means acrylate or methacrylate. The component (C) may be a polymerizable monomer. The glass transition temperature of the homopolymer obtained by polymerizing only the component (C) is preferably 200 ° C or higher.

Examples of the polyfunctional (meth) acrylate include isocyanuric acid tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

The low molecular weight imide compound having a molecular weight of less than 1,000 is represented by the following general formula (C1):

(28)

Wherein R ₃ is a single bond, a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₄ and R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, An aryl group, an alkoxy group or a halogen atom, and m is an integer of 1 or more.

Is preferably maleimide.

In the formula (C1), m may be an integer of 2 or more or an integer of 3 or more.

The low molecular weight imide compound having a molecular weight of less than 1,000 is represented by the following general formula (C2):

[Chemical Formula 29]

Wherein R ₁₁ is a single bond, a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₁₂ and R ₁₃ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, An aryl group, an alkoxy group or a halogen atom, and q is an integer of 2 to 4.

Is more preferably maleimide.

By using the low molecular weight imide compound as the component (C), a cured film excellent in adhesion after development on the polybenzoxazole resin can be obtained. The mechanism of relieving the relief pattern on the polybenzoxazole resin after development is not clear. However, in the heating process (about 100 캜) for drying the solvent at the time of forming the coating film of the relief pattern, a low molecular weight imide The compound and the polybenzoxazole resin are stacked and interacted at the resin interface so that the developer is prevented from penetrating into the interface between the coating film and the polybenzoxazole resin at the time of development or dissolution due to solvation is suppressed , It is presumed that the peeling of the relief pattern is consequently suppressed.

(C) Specific examples of the low molecular weight imide compound include 1-phenylpyrrolidine-2,5-dione, succinimide, N-pentylsuccinimide, glutazine, 2,6 (lH, 3H) -pyridinedione , N-ethylmaleimide, fluorimide, N-phenylmaleimide, N- (4-chlorophenyl) malanimide, N- (2- chlorophenyl) N-isopropylacrylamide, N-methylmalaineimide, N- (2-nitrophenyl) malaleneimide, N- (2-nitrophenyl) (2-methylphenyl) malenyl imide, 1- (2,4-dimethylphenyl) -3-pyrroline-2,5- Pyrrole-2,5-dione, N-cyclohexyl saline imide, N-butyl maleinimide, 1- (hydroxymethyl) -1H- pyrrole- Pyrrole-2,5-dione, N- (4-aminophenyl) maloneimide, 3,4-dibromo-3-pyrroline- , 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, maleimide, 2,3- (4-hydroxyphenyl) indolinone, N- (4-hydroxyphenyl) indolinone, N- (4-methoxyphenyl) maleinimide, N- (4-methoxyphenyl) indolinone, N- m-vinylphenyl) maleimide, 4 - [(2,5-dioxo-1-pyrrolyl) methyl] cyclohexanecarboxylic acid succinimidyl, eosin-5-maleimide, squalene maleimide, N- , 4,6-tribromophenyl) malene imide, benzophenone-4-maleimide, maleimide nitroxide, N- (3-nitrophenyl) 3-pyrroline-1-hexanoic acid, 3- (N-maleimidylpropionyl) biocitin, N- (2,4-dinitroanilino) N-isobutyl maleimide, N-tert-butyl maleinimide, N-octyl maleimide, N-decyl maleimide, N-decyl maleimide, Malein Amide, N-bromomethylmaleimide, N-cyanomethylmaleimide, N-ethoxymethylmaleimide, N-3-nitro-4-methylbenzylmaleimide, N-aryloxymethylmaleimide, N- N-diethylaminomethylmaleimide, N-dibutylaminomethylmaleimide, N- (1-piperidinomethyl) maleimide, N- (1-morpholinomethyl) maleimide, N- (2-ethoxyethyl) maleimide, propionic acid 2- (2,5-dioxo-3-pyrrolin-1-yl) ethyl, N- (3-acetoxypropyl) maleimide, 1- (2-hydroxypropyl) -1H-pyrrole-2,5-dione, N- N-benzylsulfonyloxymaleimide, N- (dimethylamino) maleimide, N-acetylaminomaleimide, N-acetylaminomaleimide, N- (1-morpholino) maleimide, N- (phenylsulfonyl) mal N, N '- (1, 2-phenylene) bis (maleic anhydride), N, Imide), N, N'-ethylene bis (maleic anhydride), 1,6-bismaleimide hexane, N-dodecylmaleinimide, N- (2-methoxyphenyl) N, N '- (4-methyl-1,3-phenylene) bis (maleic anhydride), 4,4'-bismaleimide diphenylmethane, N, N N, N '- [sulfonylbis (4,1-phenylene)] bis (maleic anhydride), poly (phenylene methane) maleimide, , 1,1 '- (2,2,4-trimethylhexane-1,6-diyl) bis (1H-pyrrole-2,5-dione) (1,1'- [methylenebis (2-ethyl-6-methyl-4,1-phenylene)] bis (4-maleimidobutyryloxy) succinimide, N- (8-maleimidocapryloxy) succinic acid (2-methoxyphenyl) Imide, 4 - [(2,5- Oxo-1-pyrrolyl) methyl] cyclohexane-1-carboxylic acid 3-sulfosuccinimidyl, 2,2 ', 3,3'-tetraphenyl-N, N'-ethylene dimaleimide, Maleimide, N, N ', N "- [nitrilotris (ethylene)] tris (maleic anhydride).

From the viewpoint of intermolecular interaction with the polybenzoxazole resin, the low molecular weight imide compound preferably has a cyclic structure and more preferably has an unsaturated bond in the cyclic structure. Of the low molecular weight imide compounds having an unsaturated bond in the cyclic structure, as shown by the general formula (C1) or (C2), a compound having a planarity and a maleimide structure which is likely to be stacked stericly with benzoxazole Is more preferable from the viewpoint of adhesion after development on the polybenzoxazole resin.

Among the compounds having a maleimide structure, the divalent maleimide is more preferable than the monovalent maleimide from the viewpoint that it is difficult to dissolve in the developer by the crosslinking reaction. Further, the divalent maleimide has a smaller steric hindrance than the trivalent maleimide, and is more likely to be stacked with the polybenzoxazole. Therefore, from the viewpoint of adhesion with the polybenzoxazole resin, bismaleimide is more preferable. Among them, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, 4,4'-bismaleimide diphenylmethane, or polyphenylene methane maleimide is preferable because the curing shrinkage From the viewpoint of improving the adhesion to the polyimide or the polybenzoxazole resin.

The blending amount of the component (C) is 1 to 40 parts by mass, preferably 10 to 35 parts by mass when the photosensitive resin composition contains 100 parts by mass of the resin (A) component and 0.1 to 20 parts by mass of the component (B) Wealth. When the amount of the component (C) is less than 1 part by mass, the adhesiveness is insufficient. When the amount exceeds 40 parts by mass, the cured relief pattern obtained from the composition is rejected and is suitable for applications such as a passivation film, a buffer coat film, not.

(D) a silicon-containing compound

(D) is a compound represented by the following general formula (D1):

(30)

Wherein R ₂₇ and R ₂₈ are each a C ₁ -C ₄ alkyl group, R ₂₉ is a divalent organic group of C ₁ to C ₆ , and R ₃₀ is an organic group selected from nitrogen, oxygen, and sulfur, the organic group of C ₁ ~ C ₂₀ binding to, t is an integer selected from 1, 2, and 3, u is an integer selected from 0, 1, and 2, and t and u, t + u = 3. &Lt; / RTI &gt;

Containing compound.

As R ₃₀ , specifically,

A methylamino group, an ethylamino group, an n-propylamino group, an n-butylamino group, an n-hexylamino group, an n-octylamino group, an isopropylamino group, an isobutylamino group, , Mono and dialkylamino groups such as dimethylamino group, diethylamino group, dibutylamino group and dicyclohexylamino group;

An aromatic ring-containing amino group such as a phenylamino group, a benzylamino group or a diphenylamino group;

A heterocyclic-containing amino group such as a picolyl group, an aminotriazole group, a furfuryl amino group, or a morpholino group;

An alkoxy group such as a methoxy group, an ethoxy group, an n-butoxy group, a t-butoxy group, a hexyloxy group or a cyclohexyloxy group;

An alkylaryloxy group such as a phenoxy group, a benzyloxy group or a tolyloxy group, or an arylalkyloxy group;

A furfurylalkoxy group, a 2-pyridinylethoxy group, and the like;

Alkylthio groups such as methylthio group, ethylthio group, n-butylthio group, t-butylthio group, hexylthio group and cyclohexylthio group;

Mixtures thereof, and the like.

The silicon-containing compound represented by the formula (D1) is obtained by a method of reacting an isocyanate compound with a silicon compound having an amino group, a method of reacting an isocyanate group-containing silicon compound with an amine, an alcohol or a thiol.

The compounding amount of the silicon-containing compound represented by the formula (D1) is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the resin (A), the photosensitive polyimide precursor (AX) or the polyimide precursor (AY) More preferably 0.5 to 10 parts by mass. When the silicon-containing compound represented by the formula (D1) is blended in an amount of 0.1 part by mass or more based on 100 parts by mass of the resin (A), the photosensitive polyimide precursor or the (AY) polyimide precursor, excellent adhesion is ensured and 20 parts by mass By weight or less, excellent heat resistance is maintained.

(D2) shown below in addition to the silicon-containing compound represented by the formula (D1) as the component (D)

(31)

Wherein R ₃₁ and R ₃₂ are a C ₁ -C ₄ alkyl group, R ₃₃ is a divalent organic group of C ₁ to C ₆ , v is an integer selected from 1, 2, and 3, and w is 0, 1, and 2, and v and w satisfy the relationship v + w = 3.

Is added to the photosensitive resin composition.

Examples of the silicon-containing compound represented by the formula (D2) include 3-ureide propyltriethoxysilane, 3-ureidepropyltrimethoxysilane, 3-ureidopropylethoxydimethoxysilane, 3- 3-ureidopropylmethyldimethoxysilane, 3-ureidopropylethyldiethoxysilane, 3-ureidopropylethyldimethoxysilane, 3-ureidopropylmethyldimethoxysilane, 3- Ureido propyl dimethyl ethoxy silane, 3-ureido propyl dimethyl methoxy silane, and the like, and mixtures thereof.

The amount of the silicon-containing compound represented by the formula (D2) is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the resin (A), the photosensitive polyimide precursor (AX) or the polyimide precursor (AY) More preferably 0.5 to 10 parts by mass. When the resin composition of the present invention is prepared as a photosensitive resin composition, the silicone-containing compound represented by the formula (D2) is added to the resin composition in addition to the silicone-containing compound represented by the formula (D1) It is possible to improve the resolution while improving the heat resistance.

(E) a sulfur-containing compound

(E) is a compound represented by the following general formula (E1):

(32)

Wherein R ₃₄ is a C ₁ to C ₂₀ organic group or a silicon-containing organic group, and R ₃₅ is a C ₁ to C ₂₀ organic group bonded to a thiocarbonyl group by an atom selected from nitrogen, oxygen, and sulfur .}

Containing compound.

Examples of the organic group having C ₁ to C ₂₀ as R ₃₄ include a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a tolyl group and a benzyl group. Examples of the silicon-containing organic group include trimethoxysilylpropyl Group, a triethoxysilylpropyl group, a methyldimethoxysilylpropyl group, a methyldiethoxysilylpropyl group, and a triethoxysilylethyl group.

As R ₃₅ , for example,

A methylamino group, an ethylamino group, an n-propylamino group, an n-butylamino group, an n-hexylamino group, an n-octylamino group, an isopropylamino group, an isobutylamino group, , Mono and dialkylamino groups such as dimethylamino group, diethylamino group, dibutylamino group and dicyclohexylamino group;

An aromatic ring-containing amino group such as a phenylamino group, a benzylamino group or a diphenylamino group;

A heterocyclic-containing amino group such as a picolyl group, an aminotriazole group, a furfuryl amino group, or a morpholino group;

An alkoxy group such as a methoxy group, an ethoxy group, an n-butoxy group, a t-butoxy group, a hexyloxy group or a cyclohexyloxy group;

An alkylaryloxy group such as a phenoxy group, a benzyloxy group or a tolyloxy group, or an arylalkyloxy group;

A furfurylalkoxy group, a 2-pyridinylethoxy group, and the like;

Alkylthio groups such as methylthio group, ethylthio group, n-butylthio group, t-butylthio group, hexylthio group and cyclohexylthio group;

And the like.

The blending amount of the sulfur-containing compound (E) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin (A), the photosensitive polyimide precursor (AX) or the polyimide precursor (AY) More preferably 0.5 to 10 parts by mass. (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor in an amount of 0.1 part by mass or more, excellent adhesion can be ensured, and when 20 parts by mass or less By mixing, excellent heat resistance is maintained.

Other components

The resin composition of the present invention may further contain components other than the components (A) to (E).

As the other components, a solvent may be used. In this case, the components (A) to (E) are dissolved in a solvent to obtain a varnish-like negative-working photosensitive resin composition.

As the solvent, it is preferable to use a polar organic solvent from the viewpoint of solubility in the resin (A), the photosensitive polyimide precursor (AX) or the polyimide precursor (AY). Specific examples thereof include N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, Cyclopentanone,? -Butyrolactone,? -Acetyl-? -Butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone and the like are used do. These may be used alone or in combination of two or more.

The solvent may be used in a range of, for example, 30 to 1500 parts by mass, relative to 100 parts by mass of the resin (A), the photosensitive polyimide precursor (AX) or the polyimide precursor (AY), depending on the desired coating film thickness and viscosity of the resin composition , Preferably 100 to 1000 parts by mass.

From the viewpoint of improving the storage stability of the resin composition, a solvent containing an alcohol is preferable. Examples of the alcohols include alcohols having an alcoholic hydroxyl group in the molecule and no olefinic double bond. Specific examples thereof include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n- Propyleneglycol-2-methylether, propyleneglycol-1-ethylether, propyleneglycol-2-methylpropionate, propyleneglycol-2-methylether, propyleneglycol- Propylene glycol monoalkyl ethers such as ethyl ether, propylene glycol-1- (n-propyl) ether and propylene glycol-2- (n-propyl) ether; ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n 2-hydroxyisobutyric acid esters, ethylene glycol, and propylene glycol, and the like. The. Among these, alkyl alcohols, lactic acid esters, propylene glycol monoalkyl ethers, and 2-hydroxyisobutyric acid esters are preferable. As the alkyl alcohols, ethyl alcohol is preferable. Ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, and propylene glycol-1- (n-propyl) ether are more preferable.

When the solvent contains an alcohol having no olefinic double bond, the content of the alcohol having no olefinic double bond in the total solvent is preferably 5 to 50 mass%, more preferably 10 to 30 mass% Mass%. When the content of the alcohol having no olefinic double bond is 5% by mass or more, the storage stability of the resin composition is good. When the content is 50% by mass or less, the resin (A), the photosensitive polyimide precursor (AX) The solubility of the precursor is good.

The resin composition of the present invention may further contain a resin component other than the above-mentioned (A) resin, (AX) photosensitive polyimide precursor and (AY) polyimide precursor. Examples of the resin component that can be contained include an epoxy resin, a siloxane resin, and an acrylic resin. The blending amount of these resin components is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the resin (A), the photosensitive polyimide precursor (AX) or the polyimide precursor (AY).

When the resin composition of the present invention is photosensitive, the resin composition may contain a photosensitizer other than the above-mentioned components (B1) and (B2), and may be used as a photosensitizer other than components (B1) A conventionally used photopolymerization initiator can be arbitrarily selected.

The photopolymerization initiator usually used is not limited, but, for example,

Benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone;

Acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone and 1-hydroxycyclohexyl phenyl ketone;

Thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and diethylthioxanthone;

Benzyl derivatives such as benzyl, benzyldimethyl ketal and benzyl- beta -methoxyethyl acetal;

Benzoin derivatives such as benzoin and benzoin methyl ether;

Phenyl-1,2-propanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl- (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, 1,3-diphenylpropanetri- (O-benzoyl) oxime, Irgacure OXE01 (trade name, manufactured by BASF), Irgacure OXE02 (BASF, TR-PBG305 (trade name, manufactured by Sangju Strong Electronics New Material Co., Ltd., trade name, manufactured by Sangju Kikai Kikai Kikai KK), Adeka Optomer N-1919 Oxime;

N-aryl glycines such as N-phenylglycine;

Peroxides such as benzoyl perchloride;

Aromatic biimidazoles;

.

One kind or a mixture of two or more kinds of them may be used. Of the above photosensitizers, oximes are more preferable from the viewpoint of photosensitivity.

The blending amount of the photosensitizer is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin (A), the photosensitive polyimide precursor (AX) or the polyimide precursor (AY), and 2 to 15 parts by mass . A photosensitive resin composition having excellent photosensitivity can be obtained by mixing the photosensitive agent in an amount of 0.1 part by mass or more based on 100 parts by mass of the resin (A), the photosensitive polyimide precursor (AX) or the polyimide precursor (AY) By weight or less, a photosensitive resin composition having excellent thick-film curability can be obtained.

When the resin composition of the present invention is photosensitive, a sensitizer may optionally be added to the resin composition in order to improve the light sensitivity.

Examples of sensitizers include, but are not limited to, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, 2,6- Diethylaminobenzal) cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, (P-dimethylaminophenyl) biphenylene) -benzothiazole, 2- (p-dimethyl) aminocarbonyldiimidazole, p- Aminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4'-dimethylaminobenzal) acetone, 1,3- Ethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3- ethoxycarbonyl- Oxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3- 7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, Dimethylaminobenzoic acid isoamyl, diethylaminobenzoic acid isoamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2- mercaptobenzothiazole, 2- (p- (P-dimethylaminostyryl) benzothiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d) thiazole, 2- ) Styrene, and the like. These may be used alone or in combination of 2 to 5 kinds, for example.

When the sensitizer for improving the photosensitivity is contained in the negative-type photosensitive resin composition, the blending amount of the sensitizer is preferably 100 parts by mass or more per 100 parts by mass of the resin (A), the photosensitive polyimide precursor (AX) or the polyimide precursor (AY) It is preferably 0.1 to 25 parts by mass.

In order to improve the resolution of the relief pattern, a monomer having a photopolymerizable unsaturated bond, which is different from the component (C), can be incorporated into the resin composition. As such a monomer, a (meth) acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferable, but it is preferable to use an ethylene glycol (meth) acrylate represented by diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, Or mono- or diacrylates and methacrylates of polyethylene glycols, mono- or diacrylates and methacrylates of propylene glycol or polypropylene glycols, mono-, di- or triacrylates and methacrylates of glycerol, cyclohexane diacrylates Diacrylates and dimethacrylates of 1,4-butanediol; diacrylates and dimethacrylates of 1,6-hexanediol; diacrylates and dimethacrylates of neopentyl glycol; Mono or diacrylates of bisphenol A and Methacrylate; and the like can be mentioned methacrylamide and its derivatives; benzenetricarboxylic methacrylate; isobornyl acrylate and methacrylate; acrylamide and its derivatives.

When the above-mentioned monomer having a photopolymerizable unsaturated bond is contained in the negative-type photosensitive resin composition in order to improve the resolution of the relief pattern, the amount of the monomer to be incorporated is preferably in the range of (A) resin, (AX) photosensitive polyimide precursor or AY) polyimide precursor in an amount of 1 to 50 parts by mass based on 100 parts by mass of the polyimide precursor.

In order to improve the adhesion between the film formed by using the resin composition of the present invention and the substrate, an adhesion assisting agent may be incorporated into the resin composition. Examples of the adhesion promoter include γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane , 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- ( 3-triethoxysilylpropyl) succinimide, N- [3- (triethoxysilyl) propyl] phthalamidic acid, benzophenone-3,3'-bis Amide) -4,4'-dicarboxylic acid, benzene-1,4-bis (N- [3-triethoxysilyl] propylamide) -2,5-dicarboxylic acid, 3- Silyl) propylsuccinic anhydride, N-phenylaminopropyltrimethoxysilane, and other silane coupling agents such as aluminum tris (ethyl acetoacetate), aluminum tris It may be mentioned aluminum-based adjuvants, such as adhesive acetonate), ethylacetoacetate aluminum di-isopropylate.

Of these adhesion aids, silane coupling agents are preferred from the viewpoint of adhesion. When the negative type photosensitive resin composition contains an adhesion promoter, the amount of the adhesion assisting agent is preferably in the range of 0.5 to 25 parts by mass relative to 100 parts by mass of the resin (A), the photosensitive polyimide precursor (AX) or the polyimide precursor (AY) .

A thermal polymerization inhibitor may be added to the photosensitive resin composition in order to improve stability of the viscosity and photosensitivity of the photosensitive resin composition when the composition is stored in the form of a solution containing a solvent. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2- Glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt, etc. Is used.

The blending amount of the heat polymerization inhibitor in the photosensitive resin composition is preferably in the range of 0.005 to 12 parts by mass based on 100 parts by mass of the resin (A), the photosensitive polyimide precursor (AX) or the polyimide precursor (AY).

A crosslinking agent may be added to the resin composition as desired. The crosslinking agent can crosslink the resin (A), the photosensitive polyimide precursor (AX) or the polyimide precursor (AY) when the relief pattern formed by using the resin composition of the present invention is thermally cured, A network can be formed. The crosslinking agent can further enhance the heat resistance and chemical resistance of the cured film formed from the negative-type photosensitive resin composition. As the crosslinking agent, an amino resin and a derivative thereof are preferably used. Among them, a urea resin, a glycol urea resin, a hydroxyethylene urea resin, a melamine resin, a benzoguanamine resin and derivatives thereof are more preferably used. Particularly preferred crosslinking agents are alkoxymethylated urea compounds and alkoxymethylated melamine compounds. Examples thereof include MX-290 (manufactured by Nippon Carbide Co., Ltd.), UFR-65 (manufactured by Nippon Saito KK), and MW-390 .

The amount of the crosslinking agent in the resin composition is preferably in the range of from 100 parts by mass to 100 parts by mass of the resin (A), the photosensitive polyimide precursor (AX) or the polyimide precursor (AY) in order to maintain a balance of heat resistance, chemical resistance, It is preferably 0.5 to 20 parts by mass, and more preferably 2 to 10 parts by mass. When the blending amount is 0.5 parts by mass or more, good heat resistance and chemical resistance are exhibited, and when it is 20 parts by mass or less, storage stability is excellent.

In the case of using a substrate made of copper or a copper alloy, an azole compound can be incorporated in the resin composition in order to suppress discoloration of the substrate surface. Examples of the azole compound include 1-methyl-1H-triazole, 5-methyl-1H-triazole, Phenyl-1 H- triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1- (2-dimethylaminoethyl) triazole , 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H- triazole, 1H-benzotriazole, 2- (3,5-di-t-butyl-benzotriazole), 2- [2-hydroxy- 2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl- Hydroxyphenyl benzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4 (4'-hydroxyphenyl) benzotriazole, 2- Methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, Sol, 1-methyl-1H-tetrazole, and the like. Preferred azole compounds include tolylthiazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used singly or in a mixture of two or more.

The blending amount of the azole compound in the resin composition is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin (A), the photosensitive polyimide precursor (AX) or the (AY) polyimide precursor, More preferably 5 parts by mass. When the blending amount of the azole compound to 100 parts by mass of the resin (A), the photosensitive polyimide precursor (AX) or the polyimide precursor (AY) is 0.1 parts by mass or more, the resin composition of the present invention is formed on copper or a copper alloy The discoloration of the copper or copper alloy surface is suppressed, and when it is 10 parts by mass or less, the optical sensitivity is excellent.

In order to suppress the discoloration of the surface of the substrate made of copper or a copper alloy, a hindered phenol compound can be incorporated into the resin composition. Examples of the hindered phenol compound include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butylhydroquinone, octadecyl-3- (3,5- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4'-methylenebis (2,6- butylphenol), 4,4'-thio-bis (3-methyl-6-t-butylphenol), 4,4'-butylidene- Bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol- Di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5- Hydroxy-hydrosinnamide), 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2,2'- (4-ethyl-6-t-butylphenol), pentaerythrityl tetrakis [3- (3,5- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3-hydroxy-2,6-dimethyl-4-isopropylbenzyl) -1,3,5-triazine-2,4 , 6- (1H, 3H, 5H) -thione, 1,3,5-tris (4-t- butyl- 1,3,5-tris (4-s-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5- (1H, 3H, 5H) -triene, 1,3,5-tris [4- (1-ethylpropyl) -3-hydroxy-2,6-dimethylbenzyl] - Triazine-2,4,6- (1H, 3H, 5H) -thione, 1,3,5-tris [4-triethylmethyl-3-hydroxy-2,6-dimethyl Benzyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -thione, 1,3,5-tris (3-hydroxy-2,6- (1H, 3H, 5H) -triene, 1,3,5-tris (4-t-butyl- , 5,6-trimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) (4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine- , 3H, 5H) -thione, 1,3,5-tris (4-t-butyl-6-ethyl- Tris (4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5 (1H, 3H, 5H) -triene, 1,3,5-tris (4-t-butyl-5,6-diethyl- Benzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -thione, 1,3,5-tris (4- Methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -thione, 1,3,5-tris (4- , 5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -thione, 1,3,5- 3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -thione and the like. Among them, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) 5H) -thione are preferred.

The blending amount of the hindered phenol compound is preferably from 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin (A), the photosensitive polyimide precursor (AX) or the polyimide precursor (AY) Mass part is more preferable. If the blending amount of the hindered phenolic compound to 100 parts by mass of the resin (A), the photosensitive polyimide precursor (AX) or the polyimide precursor (AY) is 0.1 part by mass or more, for example, When the resin composition is formed, discoloration and corrosion of copper or a copper alloy are prevented, and when it is 20 parts by mass or less, the optical sensitivity is excellent.

<Method of Manufacturing Cured Relief Pattern and Semiconductor Device>

When the resin composition of the present invention is photosensitive, the following steps:

(1) a step of coating the above-mentioned photosensitive resin composition on a substrate to form a photosensitive resin layer on the substrate,

(2) a step of exposing the photosensitive resin layer,

(3) developing the exposed photosensitive resin layer to form a relief pattern,

(4) a step of providing a relief pattern to a heat treatment to form a cured relief pattern

And a method for producing the cured relief pattern. Typical aspects of each process will now be described.

(1) a step of applying a photosensitive resin composition on a substrate to form a photosensitive resin layer on the substrate

In this step, the photosensitive resin composition of the present invention is coated on a substrate and, if necessary, dried to form a photosensitive resin layer. As a coating method, a method conventionally used for coating a photosensitive resin composition, for example, a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine, etc., a spray coating method using a spray coater, etc. Can be used.

If necessary, the coating film made of the photosensitive resin composition can be dried. As the drying method, a method such as drying by air drying, oven or hot plate, vacuum drying, or the like is used. The drying of the coating film is carried out under the conditions that the resin (A) in the photosensitive resin composition is modified or the photosensitive polyimide precursor (AX) and the polyimide precursor (AY) are not imidized . Concretely, when air drying or heating drying is carried out, drying can be carried out at a temperature of 20 to 140 DEG C for 1 minute to 1 hour. As described above, the photosensitive resin layer can be formed on the substrate.

(2) a step of exposing the photosensitive resin layer

In this step, the photosensitive resin layer formed as described above is exposed by a photomask or a reticle having a pattern or directly by an ultraviolet light source or the like using an exposure apparatus such as a contact aligner, a mirror projection, or a stepper.

Thereafter, a post exposure bake (PEB) and / or a pre-development bake by a combination of arbitrary temperature and time may be performed for the purpose of improving the light sensitivity and the like. The baking conditions are preferably in the range of 40 to 120 DEG C and the time is in the range of 10 seconds to 240 seconds. However, the baking conditions are not limited to this range unless they hinder the properties of the photosensitive resin composition of the present invention.

(3) a step of developing the exposed photosensitive resin layer to form a relief pattern

In this step, unexposed portions of the photosensitive resin layer after exposure are developed and removed. As a developing method for developing the photosensitive resin layer after exposure (irradiation), any one of a conventionally known developing method of a photoresist, for example, a rotary spray method, a paddle method, a dipping method accompanied by an ultrasonic treatment, . For the purpose of adjusting the shape of the relief pattern after development, post-development baking may be performed by a combination of arbitrary temperature and time, if necessary.

As the developing solution used for the development, a good solvent for the photosensitive resin composition, or a combination of a good solvent and a poor solvent is preferable. Examples of the preferable solvent include N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone,? -Butyrolactone, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate and water are preferable as the poor solvent. When a mixture of a good solvent and a poor solvent is used, it is preferable to adjust the ratio of the poor solvent to the good solvent due to the solubility of the polymer in the photosensitive resin composition. Two or more kinds of solvents may be used in combination, for example, various kinds of solvents.

(4) a step of forming a cured relief pattern by providing a relief pattern to heat treatment

In this step, the relief pattern obtained by the above-mentioned development is heated to refine the photosensitive component, and the resin (A), the photosensitive polyimide precursor (AX) or the polyimide precursor (AY) is thermally cured to form a cured relief pattern Conversion. As the method of heat curing, various methods such as a method using a hot plate, a method using an oven, and a method using a heating-up type oven capable of setting a temperature program can be selected. The heating can be carried out, for example, at 200 ° C to 400 ° C for 30 minutes to 5 hours. As the atmospheric gas at the time of heat curing, air may be used, or an inert gas such as nitrogen or argon may be used.

<Semiconductor Device>

A semiconductor device including the cured relief pattern obtained by the above-described method for producing a cured relief pattern may be provided. More specifically, it is possible to provide a semiconductor device having a substrate as a semiconductor element and a curing relief pattern of polyimide formed on the substrate by the above-described method for producing a cured relief pattern. The present invention can also be applied to a method of manufacturing a semiconductor device including a method of manufacturing a cured relief pattern described above as a part of a process using a semiconductor element as a substrate. In the semiconductor device of the present invention, the cured relief pattern can be formed by a method of manufacturing the cured relief pattern as described above, such as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device or a protective film for a semiconductor device having a bump structure And can also be manufactured by a method of producing a cured relief pattern and a known method of manufacturing a semiconductor device.

&Lt; Resin film &

As the component (A), polyimide precursors such as polyamic acid, polyamide acid ester, polyamide acid salt, polyamide acid amide, polyhydroxyamide which may be a polyoxazole precursor, polyaminoamide, polyamide, At least one resin selected from the group consisting of polyimide, polyimide, polybenzoxazole, polybenzimidazole, polybenzothiazole, and phenol resin, and has a crosslinking density of 1.0 x 10 &lt; ~ ⁴ & , 3.0 × 10 ^-3 mol / cm 3 or less, and a 5% weight reduction temperature of 250 ° C. or more and 400 ° C. or less is also one of the embodiments of the present invention.

The component (A) contained in the resin film may be the same as the resin described as the component (A) contained in the photosensitive resin composition or the resin composition. From the viewpoint of adhesion with the polybenzoxazole resin, the component (A) is preferably at least one member selected from the group consisting of polyamide acid, polyamide acid ester, polyamide acid salt, polyamide acid amide, polyamide, polyamideimide, polyimide, , Polybenzimidazole, and polybenzothiazole are preferred. In the resin film, the component (A) is preferably contained in an amount of 50 mass% or more, more preferably 70 mass% or more, relative to the total mass of all components constituting the resin film. If necessary, a resin other than the component A may be contained in the resin film.

The weight average molecular weight of the resin contained in the resin film is preferably 1,000 or more, more preferably 5,000 or more, in terms of polystyrene by gel permeation chromatography from the viewpoints of heat resistance and mechanical properties after heat treatment. The upper limit of the weight average molecular weight is preferably 100,000 or less.

The crosslinking density is the number of moles of chemically crosslinked functional groups contained in 1 cm 3 of the resin film. The crosslinking is carried out by a method in which a monomer having a crosslinkable functional group is copolymerized with the component (A) and the crosslinkable functional groups are reacted with each other, and a crosslinking agent which is chemically crosslinked with the component (A) is added to the component (A) , A method of crosslinking the molecular chains of the component (A) through the crosslinking agent, a method of adding a polyfunctional monomer to the component (A), and cross-linking the polyfunctional monomer with each other. When crosslinking occurs in the resin, the storage modulus of elasticity higher than the glass transition temperature increases with the crosslinking density. In this case, when elasticity is caused only by ideal rubber elasticity, there is a relationship between the crosslinking density and the storage elastic modulus as follows:

n = E '/ 3RT

{N: cross-link density, E ': storage elastic modulus, R: gas constant, T: absolute temperature}

Is established.

Therefore, in the case of an ideal rubber elastic body, the crosslinking density can be obtained by measuring the storage elastic modulus at or above the glass transition temperature of the resin film. The storage elastic modulus at or above the glass transition temperature can be measured using, for example, a dynamic viscoelasticity measuring apparatus. However, since the actual elastic body is an ideal rubber elastic body, the relationship between the crosslink density and the storage elastic modulus is not strictly established. In this case, if the number of crosslinkable functional groups contained in the resin film and the reaction rate thereof can be obtained by a spectroscopic method, for example, while confirming that the storage elastic modulus of the resin increases above the glass transition temperature using, for example, a dynamic viscoelasticity measuring apparatus, From this, the crosslinking density can be calculated.

The crosslinking density of the resin film used in the present invention is preferably 1.0 x 10 ^-4 mol / cm 3 or more and 3.0 × 10 ^-3 mol / cm 3 or less, preferably 3.0 × 10 ^-4 mol / cm 3 or more and 2.0 × 10 ^-3 mol / Cm &lt; 3 &gt;. When the crosslinking density is less than 1.0 x 10 &lt; ^-4 &gt; mol / cm &lt; 3 &gt;, adhesion between the resin film and the polybenzoxazole resin is insufficient. When the cross-linking density exceeds 3.0 ^10-3 mol / cm3, the resin film is retracted and is not suitable for applications such as the passivation film, the buffer coat film and the interlayer insulating film assumed in the present invention.

The 5% weight reduction temperature is obtained by raising the temperature at a rate of 10 占 폚 / min under nitrogen using a thermogravimetric analyzer. If the 5% weight reduction temperature is less than 250 占 폚, the heat resistance is too low, which is not suitable for applications such as the passivation film, the buffer coat film and the interlayer insulating film assumed in the present invention. When the 5% weight reduction temperature exceeds 400 ° C, adhesion with the polybenzoxazole resin is not sufficient.

The resin film is obtained by applying, for example, a solution in which a component that is a precursor of the resin film is dissolved, on the substrate and heating it at a temperature of 250 DEG C or less. An exposure process may be performed before heating. At this time, by forming the resin film on a substrate including a resin substrate having a glass transition temperature of 250 DEG C or lower by setting the heating temperature to 250 DEG C or lower, or by setting the heating temperature to 200 DEG C or lower, Lt; 0 &gt; C or less, to obtain a laminate.

The resin composition of the present invention is useful for applications such as the above-described semiconductor device, interlayer insulation of a multilayer circuit, a cover coat of a flexible copper clad, a solder resist film, and a liquid crystal alignment film.

Example

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. In Examples, Comparative Examples and Production Examples, the physical properties of the resin, the resin film and the resin composition were measured and evaluated by the following methods.

(1) Weight average molecular weight

The weight average molecular weight (Mw) of the resin was measured by gel permeation chromatography (in terms of standard polystyrene). The column used for the measurement was Shodex (trade name) 805M / 806M series manufactured by Showa Denko KK. Shodex STANDARD SM-105 manufactured by Showa Denko KK was selected as the standard monodisperse polystyrene, and the developing solvent was N-methyl- Pyrrolidone, and as a detector, Shodex (trade name) RI-930 manufactured by Showa Denko Co., Ltd. was used.

(2) Evaluation of adhesion to polybenzoxazole resin

A precursor or a photosensitive resin composition of a resin film was spin-coated on a 6-inch silicon wafer coated and cured with a polybenzoxazole resin and dried to form a resin film precursor or a photosensitive resin layer with a thickness of about 10 탆. This coating film was exposed to light by irradiation with energy of 1500 mJ / cm &lt; 2 &gt; using an i-line stepper NSR2005i8A (manufactured by Nikon Corporation) using a reticle having a test pattern formed thereon. Subsequently, the coated film formed on the wafer was spray-developed with a developing device (D-SPIN636 type, manufactured by Dainippon Screen, Japan) using cyclopentanone, rinsed with propylene glycol methyl ether acetate to remove unexposed portions , A resin film precursor, or a photosensitive resin composition.

The wafer having the relief pattern formed thereon was heat-treated at 200 to 300 DEG C for 2 hours under a nitrogen atmosphere using an elevated program curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Japan) A cured relief pattern of a resin film or a photosensitive resin composition was obtained on a substrate coated with a sol resin and cured. The film thickness was measured by using a Tencor P-15 type step system (manufactured by KEIL Tencor Corporation). For each of the obtained patterns, the pattern shape and the width of the pattern portion were observed under an optical microscope and evaluated according to the following criteria:

Good: The area of the obtained openings of the 20 탆 pattern is ½ or more of the openings of the corresponding pattern mask, and there is no peeling.

Bad: The area of the opening is less than 1/2 of the corresponding pattern mask opening area or there is peeling.

(3) Evaluation of taper angle of opening pattern

The photosensitive resin composition was spin coated on a 6-inch silicon wafer and dried to form a coating film having a thickness of 8.5 탆. This coating film was irradiated with energy of 500 mJ / cm &lt; 2 &gt; by means of a freeze GHI (manufactured by ULTRA TECH CO., LTD.) Through a mask having a test pattern formed thereon. Subsequently, the coated film after irradiation was spray-developed with a developing device (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd.) using cyclopentanone and rinsed with propylene glycol methyl ether acetate to develop and remove unexposed portions, &Lt; / RTI &gt;

A silicon wafer having this relief pattern was immersed in liquid nitrogen, and a 50 占 퐉 width line-and-space (1: 1) portion was cut in a direction perpendicular to the line. The obtained cross section was observed with an SEM (Hitachi High Technologies S-4800 type). Referring to Figs. 1A to 1E, taper angles were evaluated by a method including the following steps 1 to 5:

1. Drawing the top and bottom of the opening (Fig. IA);

2. Determining the height of the opening (Fig. 1B);

3. Draw a straight line (center line) parallel to the top and bottom sides beyond the center of the height (Fig. 1C);

4. Finding the intersection (center point) of the center line and the opening pattern (Figure 1D)

 ; And

5. A tangent line is drawn in accordance with the slope of the pattern at the center point, and the angle formed by the tangent line and the lower side is regarded as a taper angle (Fig. 1E).

The wafer was subjected to a heat treatment at 200 to 390 占 폚 for 2 hours under a nitrogen atmosphere using an elevated programmed cure (VF-2000 type, manufactured by Japan Koyo Lindberg Co., Ltd.) A cured relief pattern having a thickness of 4 to 5 mu m was obtained.

For this relief pattern, the film thickness was measured using a Tencor P-15 type step system (manufactured by KL-Tencor Corporation), and the taper angle of the line-and-space (1: 1) portion was obtained in the same manner as described above.

(4) Minimum aperture pattern size evaluation

The resin composition was spin coated on a 6-inch silicon wafer and dried to form a coating film having a thickness of 8.5 탆. This coating film was irradiated with energy of 500 mJ / cm &lt; 2 &gt; using a prism GHI (manufactured by ULTRA TECH CO., LTD.) Using a mask having a test pattern formed thereon. Subsequently, the coated film after irradiation was spray-developed with a developing device (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd.) using cyclopentanone and rinsed with propylene glycol methyl ether acetate to develop and remove unexposed portions, &Lt; / RTI &gt;

The wafer on which the relief pattern was formed was subjected to heat treatment at 200 to 390 占 폚 for 2 hours in a nitrogen atmosphere using a heating program cure (VF-2000 type, manufactured by Koyo Lindberg Co., Japan) And a cured relief pattern of about 4 to 5 탆 thick polyimide on the copper substrate, respectively.

The film thickness was measured by using a Tencor P-15 type step system (manufactured by KEIL Tencor Corporation). For the pattern obtained on the Si phase, the pattern shape and the width of the pattern portion were observed under an optical microscope to determine the size of the minimum opening pattern.

(5) Measurement of glass transition temperature (Tg) of the cured film

On a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness: 625 占 퐉 25 占 퐉) serving as a substrate, and on this silicon wafer were sputtered a 200 nm thick Ti film and a 400 nm thick Cu film in this order , The resin composition was spin-coated so as to have a film thickness after curing of about 4 to 5 mu m. Subsequently, when the resin composition was photosensitive, energy of 500 mJ / cm 2 was irradiated by a parallel optical mask aligner PLA-501FA (manufactured by Canon Inc., Japan). When the resin composition was not photosensitive, this irradiation was not carried out.

Thereafter, the film was heated at 200 to 390 DEG C for 2 hours in a nitrogen atmosphere to thermally cure, thereby obtaining a cured film. The obtained cured film was peeled from the wafer to obtain a cured tape.

The obtained cured tape was measured by a thermomechanical testing apparatus (TMA-50 manufactured by Shimadzu Corporation) at a load of 200 g / mm 2 and a temperature raising rate of 10 ° C / min at a temperature of 20 to 500 ° C. The tangential intersection of the thermal yield point of the cured tape in the measurement chart taken was taken as the glass transition temperature (Tg).

(6) Measurement of Si adhesion and Cu adhesion of the cured film

On a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness: 625 占 퐉 25 占 퐉) serving as a substrate, and on this silicon wafer were sputtered a 200 nm thick Ti film and a 400 nm thick Cu film in this order , The resin composition was spin-coated so as to have a film thickness after curing of about 4 to 5 mu m. Subsequently, when the resin composition was photosensitive, energy of 500 mJ / cm 2 was irradiated by a parallel optical mask aligner PLA-501FA (manufactured by Canon Inc., Japan). When the resin composition was not photosensitive, this irradiation was not carried out.

Thereafter, the film was heated at 200 ° C to 390 ° C for 2 hours in a nitrogen atmosphere to thermally cure the film to obtain a cured film.

The adhesion of the obtained cured film to Si or Cu was evaluated by a crosscut test (JIS K5400). That is, a cutter knife was cut on the coating film so that 100 squares with a width of 1 mm were formed, and a cellophane (registered trademark) tape was stuck thereon from the top. After adhering to the cellophane tape until bubbles disappeared, (Registered trademark) tape, and the number of squares remaining on the substrate was calculated.

(7) Crosslink density

After the resin film was peeled off from the substrate, the temperature was raised from 30 占 폚 to 400 占 폚 at 5 占 폚 / min by using a dynamic viscoelasticity measuring device Leo Vibron Model DDV-01FP (Orientech) At a frequency of Hz, minute vibration was applied to obtain a storage elastic modulus at each temperature. Further, the reaction rate of the crosslinking group in the resin film was determined by using a 380 type FTIR (manufactured by Nicolas Co.), and the crosslinking density was calculated from the reaction rate.

(8) 5% weight reduction temperature

After the resin film was peeled from the substrate, the temperature was raised from 30 占 폚 to 500 占 폚 under nitrogen at 10 占 폚 / min using a thermogravimetric analyzer (Shimadzu Corporation, TGA-50) I got it.

&Lt; Preparation Example 1 &

(Synthesis of polyimide precursor A (polymer A) as component (A)

155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2-liter separable flask, and 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of? -Butyrolactone were placed, And 81.5 g of pyridine was added with stirring to obtain a reaction mixture. After termination of the heat generation due to the reaction, the mixture was allowed to cool to room temperature and allowed to stand for 16 hours.

Next, under ice-cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of? -Butyrolactone was added to the reaction mixture over 40 minutes while stirring, and then 4,4'-di 93.0 g of minodiphenyl ether (DADPE) was suspended in 350 ml of? -Butyrolactone and added with stirring over 60 minutes. After stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour, and then 400 ml of? -Butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

The resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate comprising the crude polymer. The resulting crude polymer was separated by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer. The obtained precipitate was separated by filtration and then vacuum-dried to obtain a powdery polymer (polyimide precursor A (hereinafter also referred to as "polymer A")). The molecular weight of the polyimide precursor A was measured by gel permeation chromatography (in terms of standard polystyrene), and as a result, the weight average molecular weight (Mw) was 20,000.

&Lt; Preparation Example 2 &

(Synthesis of polyimide precursor B (polymer B) as component (A)

Except that 147.1 g of 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride was used in place of 155.1 g of 4,4'-oxydiphthalic dianhydride of Production Example 1, , A polyimide precursor B (hereinafter also referred to as &quot; polymer B &quot;) was obtained. The molecular weight of the polyimide precursor B was measured by gel permeation chromatography (in terms of standard polystyrene), and as a result, the weight average molecular weight (Mw) was 22,000.

&Lt; Preparation Example 3 &

(Synthesis of polyamic acid (polymer C)

93.0 g of 4,4'-diaminodiphenyl ether (DADPE) was placed in a 2-liter separable flask, 400 ml of N-methylpyrrolidone was added, and the mixture was stirred and dissolved at room temperature. Thereafter, 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was added and reacted at 80 DEG C for 5 hours to obtain a solution of polymer C (polyamic acid as a polyimide precursor). The molecular weight of the polymer A-1 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight average molecular weight (Mw) was 20,000.

&Lt; Preparation Example 4 &

(Synthesis of silicon-containing compound D-1)

In a 500 ml three-necked flask, 10.2 g of hexylamine was added and 146.4 g of N-methylpyrrolidone was added and dissolved. 26.4 g of 3-ureide propyltriethoxysilane was then added dropwise from a dropping funnel, Followed by stirring for 5 hours to obtain a solution of the silicon-containing compound D-1.

&Lt; Example 1 &gt;

A photosensitive resin composition was prepared by using the polyimide precursor A (polymer A) and the polyimide precursor B (polymer B) in the following manner, and the prepared composition was evaluated. 50 g of Polymer A and 50 g of Polymer B as the component (A), 50 g of Polymer A as Adeka optomer NCI831 (product of ADEKA, trade name, 0.001 wt% solution, g line, h line, 2 g each of 0, 0.13, and 0.22), 10 g of 4,4'-bismaleimide diphenylmethane as the component (C), 4 g of hexamethoxymethylmelamine and 4 g of tetraethylene glycol dimethacrylate 8 g of N-methylpyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate (hereinafter referred to as &quot; NMP &quot;) were added together with 3 g of silicon-containing compound D- g. &lt; / RTI &gt; The viscosity of the obtained solution was adjusted to about 35 poises by further adding a small amount of the mixed solvent to obtain a photosensitive resin composition.

The composition was applied to a silicon wafer according to the above-described (2) method for evaluating adhesion with a polybenzoxazole resin, followed by drying, and exposure to polybenzoxazole (PBO) resin The adhesion on the substrate was &quot; good &quot;.

&Lt; Example 2 &gt;

The negative-type photosensitive resin composition was prepared by changing the compounding amount of 4,4'-bismaleimide diphenylmethane as the component (C) in Example 1 to 20 g, and the same evaluation as in Example 1 was conducted . The adhesion on the PBO resin substrate was evaluated as &quot; good &quot;. At this time, the composition had a heat curing temperature of 200 占 폚.

&Lt; Example 3 &gt;

A photosensitive resin composition was prepared by changing the component (C) in Example 1 to bis (3-ethyl-5-methyl-4-maleimidephenyl) methane to give the same evaluation as in Example 1 did. The adhesion on the PBO resin substrate was evaluated as &quot; good &quot;. At this time, the composition had a heat curing temperature of 200 占 폚.

<Example 4>

A photosensitive resin composition was prepared by changing the compounding amount of bis (3-ethyl-5-methyl-4-maleimide phenyl) methane as the component (C) in Example 3 to 20 g, . The adhesion on the PBO resin substrate was evaluated as &quot; good &quot;. At this time, the composition had a heat curing temperature of 200 占 폚.

&Lt; Example 5 &gt;

The component (C) in Example 1 of the present invention was changed to N-phenylmaleimide to prepare a photosensitive resin composition, and the same evaluations as in Example 1 were carried out. The adhesion on the PBO resin substrate was evaluated as &quot; good &quot;. At this time, the composition had a heat curing temperature of 200 占 폚.

&Lt; Example 6 &gt;

A photosensitive resin composition was prepared by changing the component (C) in Example 1 to N, N ', N "- [nitrilotrol (ethylene)] tris (maleene imide) The same evaluation as in Example 1 was carried out. The adhesion on the PBO resin substrate was evaluated as &quot; good &quot;. At this time, the composition had a heat curing temperature of 200 占 폚.

&Lt; Example 7 &gt;

In Example 2, a photosensitive resin composition was prepared by changing the component (C) in the present invention to isocyanuric acid triacrylate, which is a multifunctional methacrylate having a glass transition temperature of 200 占 폚 or higher of the homopolymer , And the same evaluation as in Example 2 was carried out. The adhesion on the PBO resin substrate was evaluated as &quot; good &quot;. At this time, the composition had a heat curing temperature of 200 占 폚.

&Lt; Comparative Example 1 &

4,4'-bismaleimide diphenylmethane as the component (C) in the present invention in Example 1 was taken out to prepare a negative-working photosensitive resin composition, and the same evaluations as in Example 1 were carried out. The adhesion property on the PBO resin substrate was evaluated as &quot; poor &quot;. At this time, the composition had a heat curing temperature of 200 占 폚.

The evaluation results of Examples 1 to 7 and Comparative Example 1 are shown in Table 1 below.

Explanation of the abbreviations in Table 1

B1: Adeka Optomer NCI831 (trade name, manufactured by ADEKA)

C1: 4,4'-bismaleimide diphenylmethane

C2: Bis (3-ethyl-5-methyl-4-maleimidophenyl) methane

C3: N-phenylmaleimide

C4: N, N ', N "- [nitrile tris (ethylene)] tris (maleic anhydride)

C5: Isocyanuric acid triacrylate

D1: Silicon-containing compound D-1

&Lt; Example 8 &gt;

50 g of the polymer A and 50 g of the polymer B as the component (AX) and Irgacure OXE03 (product of BASF, trade name, 0.001 wt% solution, g line, h line and i line absorbance as the component (B) , 0, and 0.27), 8 g of tetraethylene glycol dimethacrylate, 0.05 g of 2-nitroso-1-naphthol and 5 g of diphenylacetamide, N- (3- (triethoxysilyl) (0.5 g), and benzophenone-3,3'-bis (N- (3-triethoxysilyl) propylamide) -4,4'-dicarboxylic acid The solution was dissolved in a mixed solvent (weight ratio 8: 2) consisting of an aqueous solution of sodium hydroxide, potassium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydroxide, and potassium hydroxide.

This composition was evaluated by the above-described (3) taper angle evaluation of the opening pattern and (4) the minimum opening pattern size evaluation method.

&Lt; Example 9 &gt;

50 g of Polymer A and 50 g of Polymer B as component (AX), 2 g of Irgacure OXE03 as component (B), 16 g of 4,4'-bismaleimide diphenylmethane as component (C), 10 g of tetraethylene glycol 8 g of dimethacrylate, 0.05 g of 2-nitroso-1-naphthol, 5 g of diphenylacetamide, 0.5 g of N- (3- (triethoxysilyl) propyl) phthalamidic acid, , 0.5 g of 3'-bis (N- (3-triethoxysilyl) propylamide) -4,4'-dicarboxylic acid was dissolved in a mixed solvent of N-methylpyrrolidone and ethyl lactate (weight ratio 8: 2), and the amount of the solvent was adjusted so that the viscosity became about 35 poises to obtain a photosensitive resin composition solution.

This composition was evaluated by the same method as in Example 8. [

&Lt; Example 10 &gt;

The g-line, h-line, and i-line absorbances of ADEKA OPTOMER NCI831 (trade name, trade name, manufactured by ADEKA, Inc., 0.001 wt% solution) were respectively 0 , 0.13, and 0.22) were used in place of the above-mentioned photosensitive resin composition solution.

This composition was evaluated by the same method as in Example 8. [

&Lt; Example 11 &gt;

The g-line, h-line, and i-line absorbance of TR-PBG340 (trade name, trade name, manufactured by Sangho Power Electronics Co., Ltd., 0.001 wt% solution) as the component (B) in Example 9 were 0.04, 0.06, and 0.04 ) Was used instead of 2 g of the photosensitive resin composition.

This composition was evaluated by the same method as in Example 8. [

&Lt; Comparative Example 2 &

The g-line, h-line, and i-line absorbances of the TR-PBG304 (trade name, trade name, manufactured by Sangho Power Electronics Co., Ltd., trade name: 0.001 wt% solution) as the substitute component of the component (B) , And 0.12) was used instead of the photopolymerizable resin composition of Example 8.

This composition was evaluated by the same method as in Example 8. [

The evaluation results of Examples 8 to 11 and Comparative Example 2 are shown in Table 2 below.

Explanation of the abbreviations in Table 2

- Component (B)

B1: Irgacure OXE03 (trade name, manufactured by BASF)

B2: Adeka Optomer NCI831 (trade name, manufactured by ADEKA)

B3: TR-PBG340 (trade name, manufactured by Changzhou Power Electronics Co., Ltd.)

- Component (C)

C1: 4,4'-bismaleimide diphenylmethane

- Substituent -

B4: TR-PBG304 (trade name, manufactured by Changzhou Power Electronics Co., Ltd.)

&Lt; Example 12 &gt;

3 g of a silicon-containing compound D-1 as a component (B), Irgacure OXE03 (trade name, manufactured by BASF Corporation) as a component (AY) Ethyl (mass ratio 8: 2), and adjusting the amount of the solvent so that the viscosity became about 35 poises, to obtain a resin composition.

This resin composition was evaluated by the above-described (5) measurement of the glass transition temperature (Tg) of the cured film, (6) measurement of Si and Cu adhesion of the cured film, and (4) minimum opening pattern size evaluation method.

&Lt; Example 13 &gt;

4 g of Irgacure OXE03 (trade name, manufactured by BASF Corporation) as a component (B), 3 g of a silicone-containing compound D-1 as a component (D), 50 g of polymer A as a component (AY) 8 g of glycol dimethacrylate, 0.05 g of 2-nitroso-1-naphthol and 5 g of diphenylacetamide were dissolved in a mixed solvent (weight ratio 8: 2) consisting of N-methylpyrrolidone and ethyl lactate , And the amount of the solvent was adjusted so that the viscosity became about 35 poise, thereby obtaining a resin composition.

This resin composition was evaluated by the above-described (5) measurement of the glass transition temperature (Tg) of the cured film, (6) measurement of Si and Cu adhesion of the cured film, and (4) minimum opening pattern size evaluation method.

&Lt; Example 14 &gt;

, 4 g of Irgacure OXE3 (trade name, manufactured by BASF) as a component (B), 3 g of a silicone-containing compound D-1 as a component (D) and 50 g of a polymer B as a component (A) -1160 (a 50 mass% solution of 3-ureide propyltriethoxysilane, manufactured by Momentive Company) as a methanol solution, 8 g of tetraethylene glycol dimethacrylate, 0.05 g of 2-nitroso-1-naphthol And 5 g of diphenylacetamide were dissolved in a mixed solvent (weight ratio 8: 2) consisting of N-methylpyrrolidone and ethyl lactate and the amount of the solvent was adjusted so that the viscosity became about 35 poises. .

This resin composition was evaluated by the above-described (5) measurement of the glass transition temperature (Tg) of the cured film, (6) measurement of Si and Cu adhesion of the cured film, and (4) minimum opening pattern size evaluation method.

&Lt; Example 15 &gt;

A cured film was formed and evaluated in the same manner as in Example 14 except that the heating temperature for curing was changed from 200 占 폚 to 390 占 폚.

&Lt; Example 16 &gt;

50 g of Polymer A and 50 g of Polymer B as component (AY), 4 g of Adeka Optomer NCI831 (trade name, manufactured by ADEKA Corporation) as component (B), 4,4'-bismaleimide diphenyl 3 g of a silicon-containing compound D-1 as a component (D) and 3 g of A-1160 (a 50 mass% solution of 3-ureide propyltriethoxysilane, manufactured by Momentive Company) as a methanol solution, 8 g of ethylene glycol dimethacrylate, 0.05 g of 2-nitroso-1-naphthol and 5 g of diphenylacetamide was added to a mixed solvent (weight ratio 8: 2) consisting of N-methylpyrrolidone and ethyl lactate And the amount of the solvent was adjusted so that the viscosity became about 35 poises, to obtain a resin composition.

This resin composition was evaluated by the above-described (5) measurement of the glass transition temperature (Tg) of the cured film, (6) measurement of Si and Cu adhesion of the cured film, and (4) minimum opening pattern size evaluation method.

&Lt; Example 17 &gt;

The same procedure as in Example 16 was carried out except that the component (C) in Example 16 was changed from 4,4'-bismaleimide diphenylmethane to bis (3-ethyl-5-methyl-4-maleimidophenyl) To obtain a resin composition.

This resin composition was evaluated by the above-described (5) measurement of the glass transition temperature (Tg) of the cured film, (6) measurement of Si and Cu adhesion of the cured film, and (4) minimum opening pattern size evaluation method.

&Lt; Example 18 &gt;

A resin composition was obtained in the same manner as in Example 16 except that 3 g of dicyclohexylthiourea was used as the component (E) instead of the component (D).

This resin composition was evaluated by the above-described (5) measurement of the glass transition temperature (Tg) of the cured film, (6) measurement of Si and Cu adhesion of the cured film, and (4) minimum opening pattern size evaluation method.

&Lt; Comparative Example 3 &

In Example 12, 0.5 g of N- (3- (triethoxysilyl) propyl) phthalamidic acid and 0.5 g of benzophenone-3,3'-bis (N- (3-tri Propylamido) -4,4'-dicarboxylic acid (0.5 g) was used in place of the compound (B).

This resin composition was evaluated by the above-described (5) measurement of the glass transition temperature (Tg) of the cured film, (6) measurement of Si and Cu adhesion of the cured film, and (4) minimum opening pattern size evaluation method.

&Lt; Comparative Example 4 &

In Example 14, 0.5 g of N- (3- (triethoxysilyl) propyl) phthalamidic acid and 0.5 g of benzophenone-3,3'-bis (N- (3-tri Propylamido) -4,4'-dicarboxylic acid (0.5 g) was used in place of the compound (B).

This resin composition was evaluated by the above-described (5) measurement of the glass transition temperature (Tg) of the cured film, (6) measurement of Si and Cu adhesion of the cured film, and (4) minimum opening pattern size evaluation method.

&Lt; Comparative Example 5 &

In Example 15, 0.5 g of N- (3- (triethoxysilyl) propyl) phthalamidic acid and 0.5 g of benzophenone-3,3'-bis (N- (3-tri Propoxyl) -4,4'-dicarboxylic acid (0.5 g) was used in place of the compound (B).

This resin composition was evaluated by the above-described (5) measurement of the glass transition temperature (Tg) of the cured film, (6) measurement of Si and Cu adhesion of the cured film, and (4) minimum opening pattern size evaluation method.

The evaluation results of Examples 12 to 18 and Comparative Examples 3 to 5 are shown in Table 3 below.

Explanation of the abbreviations in Table 3

B1: Irgacure OXE03 (trade name, manufactured by BASF)

B2: Adeka Optomer NCI831 (trade name, manufactured by ADEKA)

C1: 4,4'-bismaleimide diphenylmethane

C2: Bis (3-ethyl-5-methyl-4-maleimidophenyl) methane

D1: Silicon-containing compound D-1

D2: Silicon-containing compound D-1 / A-1160 (50% solution of 3-ureidopropyltriethoxysilane, manufactured by Momentive Company)

D3: N- (3- (triethoxysilyl) propyl) phthalamidic acid / benzophenone-3,3'-bis (N- (3-triethoxysilyl) propylamide) -4,4'- Malic acid

&Lt; Example 19 &gt;

50 g of Polymer A and 50 g of Polymer B as the component (A), 50 g of Polymer A as the component (A), and the g-line, h-line and i-line absorbance of ADEKA OPTOMER NCI831 (trade name, And 0.22), together with 10 g of 4,4'-bismaleimide diphenylmethane, 3 g of silicon containing compound D-1 and 0.05 g of 2-nitroso-1-naphthol were added N-methylpyrrolidone (Hereinafter referred to as NMP) and 20 g of ethyl lactate to obtain a solution. The viscosity of the obtained solution was adjusted to about 35 poises by further adding a small amount of the mixed solvent to obtain a photosensitive resin composition.

The composition was coated on a silicon wafer in accordance with the above-described (2) method for evaluating adhesion with a polybenzoxazole resin, followed by drying, exposure, development and thermal curing at 200 占 폚 to obtain a resin film. At this time, the adhesion on the polybenzoxazole (PBO) resin substrate was "good".

The crosslinking density (7) described above was obtained from the reaction rate, composition and density of maleimide by IR at 7.0 × 10 ^-4 mol / cm 3. The storage elastic modulus at 110 Hz and 300 ° C was 0.08 GPa, and the above-mentioned (8) 5% weight reduction temperature was 340 ° C.

&Lt; Example 20 &gt;

A photosensitive resin composition was prepared in the same manner as in Example 19 except that the amount of 4,4'-bismaleimide diphenylmethane added was changed to 20 g.

The composition was coated on a silicon wafer in accordance with the above-described (2) method for evaluating adhesion with a polybenzoxazole resin, followed by drying, exposure, development and thermal curing at 200 占 폚 to obtain a resin film. At this time, the adhesion on the polybenzoxazole (PBO) resin substrate was "good".

The above (7) crosslinking density was obtained from the reaction rate, composition and density of maleimide by IR at 1.4 × 10 ^-3 mol / cm 3. The storage elastic modulus at 110 Hz and 300 ° C was 0.16 GPa, and the above-mentioned (8) 5% weight reduction temperature was 370 ° C.

&Lt; Comparative Example 6 &gt;

In Example 19, a resin composition was combined in the same manner as in Example 19 except that 4,4'-bismaleimide diphenylmethane was not added, and a thermosetting resin film of the composition was obtained. At this time, the adhesiveness on the polybenzoxazole (PBO) resin substrate evaluated by the above-mentioned (2) evaluation method of adhesion with polybenzoxazole resin was "poor".

The above (7) crosslinking density was obtained from the reaction rate, composition and density of maleimide by IR at 0 mol / cm 3. The storage elastic modulus at 110 Hz and 300 ° C was 0.02 GPa, and the above-mentioned (8) 5% weight reduction temperature was 320 ° C.

The evaluation results of Examples 19 and 20 and Comparative Example 6 are shown in Table 4 below.

The resin composition and the resin film of the present invention can be preferably used in the field of photosensitive materials useful for the production of electric and electronic materials such as semiconductor devices, multilayer wiring boards and the like.

Claims (39)

The following ingredients:
(A) a polyimide precursor which is a polyamide acid, a polyamide acid ester, a polyamide acid salt, a polyamide acid amide, a polyhydroxyamide which may be a polyoxazole precursor, a polyaminoamide, a polyamide, a polyamideimide, At least one resin selected from the group consisting of polybenzoxazole, polybenzimidazole, polybenzothiazole, and phenol resin;
(B) a photosensitizer; and
(C) at least one member selected from the group consisting of polyfunctional (meth) acrylates and low molecular weight imide compounds having a molecular weight of less than 1000;
. The method according to claim 1,
Wherein the component (A) is at least one selected from the group consisting of polyamide acid, polyamide acid ester, polyamide acid salt, polyamide acid amide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, Wherein the photosensitive resin composition is at least one resin selected from the group consisting of polybenzothiazole. 3. The method according to claim 1 or 2,
Wherein the component (C) is a low molecular weight imide compound having a molecular weight of less than 1,000. 4. The method according to any one of claims 1 to 3,
Wherein the component (A) is a compound represented by the following general formula (A1):
[Chemical Formula 1]

{Wherein, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, l is an integer of 2 ~ 150, R ₁ and R ₂ are, each independently, a hydrogen atom, or a radical Is a polymerizable monovalent organic group. Provided that both of R ₁ and R ₂ are not hydrogen atoms at the same time.
Is a polyimide precursor represented by the following formula
Wherein the component (C) is a compound represented by the following general formula (C1):
(2)

Wherein R ₃ is a single bond, a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₄ and R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, An aryl group, an alkoxy group or a halogen atom, and m is an integer of 1 or more.
&Lt; / RTI &gt; 5. The method according to any one of claims 1 to 4,
Wherein the component (A) is a compound represented by the following general formula (A2):
(3)

Wherein, in the formula, X ₂ is a tetravalent organic group, Y ² is a divalent organic group, n is an integer of 2 to 150, R ₆ and R ₇ are each independently a hydrogen atom, Formula (A3):
[Chemical Formula 4]

(Wherein R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer of 2 to 10)
, Or a saturated aliphatic group having 1 to 4 carbon atoms. Provided that both of R &lt; ₆ &gt; and R &lt; ₇ &gt; are not simultaneously hydrogen atoms.
Is a polyimide precursor. 6. The method according to any one of claims 1 to 5,
Wherein the component (C) is a compound represented by the following general formula (C2):
[Chemical Formula 5]

Wherein R ₁₁ is a single bond, a hydrogen atom or an organic group having 1 to 3 carbon atoms, R ₁₂ and R ₁₃ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, An aryl group, an alkoxy group or a halogen atom, and q is an integer of 2 to 4.
&Lt; / RTI &gt; 7. The method according to any one of claims 1 to 6,
Wherein the component (B) is a oxime-based photopolymerization initiator. 8. The method according to any one of claims 1 to 7,
Wherein the component (B) comprises the following components (B1) and (B2):
An oxime ester compound in which the i-line absorbance of the 0.001 wt% solution of (B1) is 0.15 to 0.5, and the g-line absorbance and the h-ray absorbance of the 0.001 wt% solution are 0.2 or less;
(B2) an oxime ester compound having an i-line absorbance of not more than 0.1 and a g line absorbance or a h line absorbance of not less than 0.05 in a 0.001 wt% solution;
And at least one member selected from the group consisting of a photopolymerization initiator and a photopolymerization initiator. 9. The method of claim 8,
The i-line absorbance of the 0.001 wt% solution of the component (B1) is 0.15 to 0.35. 10. The method according to claim 8 or 9,
Wherein the component (B1) is a compound represented by the following general formula (B11) and (B12):
[Chemical Formula 6]

Wherein R ₁₄ is a fluorine-containing alkyl group having ₁ to ₁₀ carbon atoms, and R ₁₅ , R ₁₆ and R ₁₇ are each independently a C ₁ to C ₂₀ alkyl group, a C ₃ to C ₂₀ cycloalkyl group, A C ₆ to C ₂₀ aryl group, or a C ₁ to C ₂₀ alkoxy group, and r is an integer of 0 to 5.
(7)

{Wherein, R ₁₈ is a divalent organic group of _{C 1 ~ C 30, R 19} ~ R 26 are, each independently, C ₁ ~ C ₂₀ alkyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ An aryl group of C ₂₀ , or an alkoxy group of C ₁ to C ₂₀ , and s is an integer of 0 to 3.
And an oxime ester compound represented by the following general formula (1). 11. The method according to any one of claims 1 to 10,
In addition to the above components (A) to (C)
(D) a compound represented by the following general formula (D1):
[Chemical Formula 8]

Wherein R ₂₇ and R ₂₈ are C ₁ -C ₄ alkyl groups, R ₂₉ is a divalent organic group of C ₁ to C ₆ , and R ₃₀ is selected from the group consisting of nitrogen, oxygen, and sulfur a C organic group of ₁ ~ C ₂₀ binding to the carbonyl group by an atom, t is an integer selected from 1, 2, and 3, u is an integer selected from 0, 1, and 2, and t and u , t + u = 3 are satisfied.
And a silicon-containing compound represented by the following general formula (1). 12. The method of claim 11,
(D2) shown below in addition to the silicon-containing compound represented by the formula (D1) as the component (D)
[Chemical Formula 9]

Wherein R ₃₁ and R ₃₂ are a C ₁ -C ₄ alkyl group, R ₃₃ is a divalent organic group of C ₁ to C ₆ , v is an integer selected from 1, 2, and 3, and w is 0, 1, and 2, and v and w satisfy the relationship v + w = 3.
Wherein the photosensitive resin composition further comprises a silicon-containing compound. 11. The method according to any one of claims 1 to 10,
In addition to the above components (A) to (C)
(E) represented by the following general formula (E1):
[Chemical formula 10]

Wherein R ₃₄ is a C ₁ to C ₂₀ organic group or a silicon-containing organic group and R ₃₅ is a C ₁ to C ₂₀ group bonded with a thiocarbonyl group by an atom selected from the group consisting of nitrogen, oxygen, .
And a sulfur-containing compound represented by the following general formula (1). 11. The method according to any one of claims 1 to 10,
With respect to 100 parts by mass of the component (A)
0.1 to 20 parts by mass of the component (B)
1 to 40 parts by mass of the component (C);
Wherein the photosensitive resin composition is a photosensitive resin composition. 11. The method according to any one of claims 1 to 10,
With respect to 100 parts by mass of the component (A)
0.1 to 20 parts by mass of the component (B)
10 to 35 parts by mass of the component (C);
Wherein the photosensitive resin composition is a photosensitive resin composition. 13. The method according to claim 11 or 12,
With respect to 100 parts by mass of the component (A)
0.1 to 20 parts by mass of the component (B);
1 to 40 parts by mass of the component (C)
0.1 to 20 parts by mass of the component (D);
Wherein the photosensitive resin composition is a photosensitive resin composition. 13. The method according to claim 11 or 12,
With respect to 100 parts by mass of the component (A)
0.1 to 20 parts by mass of the component (B);
10 to 35 parts by mass of the component (C)
0.1 to 20 parts by mass of the component (D);
Wherein the photosensitive resin composition is a photosensitive resin composition. 14. The method of claim 13,
With respect to 100 parts by mass of the component (A)
0.1 to 20 parts by mass of the component (B);
1 to 40 parts by mass of the component (C)
0.1 to 20 parts by mass of the component (E);
Wherein the photosensitive resin composition is a photosensitive resin composition. 14. The method of claim 13,
With respect to 100 parts by mass of the component (A)
0.1 to 20 parts by mass of the component (B);
10 to 35 parts by mass of the component (C)
0.1 to 20 parts by mass of the component (E);
Wherein the photosensitive resin composition is a photosensitive resin composition. The following ingredients:
(AX) photosensitive polyimide precursor;
The following components (B1) and (B2)
(B1) an oxime ester compound in which the i-line absorbance of the 0.001 wt% solution is from 0.15 to 0.5, and the g-line absorbance and h-line absorbance of the 0.001 wt% solution are 0.2 or less, and
(B2) 0.001 wt% solution having an i-line absorbance of 0.1 or less and a g line absorbance or h line absorbance of 0.001 wt% solution of 0.05 or more,
At least one member selected from the group consisting of
And a photosensitive resin composition. 21. The method of claim 20,
Wherein the component (AX) is a compound represented by the following general formula (A2):
(11)

Wherein, in the formula, X ₂ is a tetravalent organic group, Y ² is a divalent organic group, n is an integer of 2 to 150, R ₆ and R ₇ are each independently a hydrogen atom, Formula (A3):
[Chemical Formula 12]

(Wherein R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer of 2 to 10)
, Or a saturated aliphatic group having 1 to 4 carbon atoms. Provided that both of R &lt; ₆ &gt; and R &lt; ₇ &gt; are not simultaneously hydrogen atoms.
Is a polyimide precursor. 22. The method according to claim 20 or 21,
And the i-line absorbance of the 0.001 wt% solution of the component (B1) is 0.15 to 0.35. 23. The method according to any one of claims 20 to 22,
Wherein the component (B1) is a compound represented by the following general formula (B11) and (B12):
[Chemical Formula 13]

Wherein R ₁₄ is a fluorine-containing alkyl group having ₁ to ₁₀ carbon atoms, and R ₁₅ , R ₁₆ and R ₁₇ are each independently a C ₁ to C ₂₀ alkyl group, a C ₃ to C ₂₀ cycloalkyl group, A C ₆ to C ₂₀ aryl group, or a C ₁ to C ₂₀ alkoxy group, and r is an integer of 0 to 5.
[Chemical Formula 14]

{Wherein, R ₁₈ is a divalent organic group of _{C 1 ~ C 30, R 19} ~ R 26 are, each independently, C ₁ ~ C ₂₀ alkyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ An aryl group of C ₂₀ , or an alkoxy group of C ₁ to C ₂₀ , and s is an integer of 0 to 3.
And an oxime ester compound represented by the following general formula (1). 24. The method according to any one of claims 20 to 23,
Wherein the total content of the components (B1) and (B2) relative to 100 parts by mass of the component (AX) is 0.1 to 10 parts by mass. 25. The method according to any one of claims 20 to 24,
Wherein the total content of the component (B1) and the component (B2) relative to 100 parts by mass of the component (AX) is 0.5 to 5 parts by mass. The following ingredients:
(AY) polyimide precursor; and
(D) a compound represented by the following general formula (D1):
[Chemical Formula 15]

Wherein R ₂₇ and R ₂₈ are C ₁ -C ₄ alkyl groups, R ₂₉ is a divalent organic group of C ₁ to C ₆ , and R ₃₀ is selected from the group consisting of nitrogen, oxygen, and sulfur a C organic group of ₁ ~ C ₂₀ binding to the carbonyl group by an atom, t is an integer selected from 1, 2, and 3, u is an integer selected from 0, 1, and 2, and t and u , t + u = 3 are satisfied.
A silicon-containing compound represented by the formula
. &Lt; / RTI &gt; 27. The method of claim 26,
(D2) shown below in addition to the silicon-containing compound represented by the formula (D1) as the component (D)
[Chemical Formula 16]

Wherein R ₃₁ and R ₃₂ are a C ₁ -C ₄ alkyl group, R ₃₃ is a divalent organic group of C ₁ to C ₆ , v is an integer selected from 1, 2, and 3, and w is 0, 1, and 2, and v and w satisfy the relationship v + w = 3.
Further comprising a silicon-containing compound represented by the following general formula (1). The following ingredients:
(AY) polyimide precursor; and
(E) represented by the following general formula (E1):
[Chemical Formula 17]

Wherein R ₃₄ is a C ₁ -C ₂₀ organic group or a silicon-containing organic group and R ₃₅ is a C ₁ -C ₂₀ alkyl group which is bonded to a thiocarbonyl group by an atom selected from the group consisting of nitrogen, oxygen and sulfur .
A sulfur-containing compound represented by the following formula
. &Lt; / RTI &gt; 29. The method according to any one of claims 26 to 28,
Wherein the component (AY) is a compound represented by the following general formula (A2):
[Chemical Formula 18]

Wherein, in the formula, X ₂ is a tetravalent organic group, Y ² is a divalent organic group, n is an integer of 2 to 150, R ₆ and R ₇ are each independently a hydrogen atom, Formula (A3):
[Chemical Formula 19]

(Wherein R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and p is an integer of 2 to 10)
, Or a saturated aliphatic group having 1 to 4 carbon atoms. Provided that both of R &lt; ₆ &gt; and R &lt; ₇ &gt; are not simultaneously hydrogen atoms.
Is a polyimide precursor. 28. The method of claim 27,
With respect to 100 parts by mass of the component (AY)
0.1 to 20 parts by mass of the component (D1)
0.1 to 20 parts by mass of the component (D2);
. &Lt; / RTI &gt; 30. The method of claim 28 or 29,
, And 0.1 to 20 parts by mass of the component (E) relative to 100 parts by mass of the component (AY). 32. The method according to any one of claims 26 to 31,
(B) a photosensitizer. The following:
(1) A process for producing a photosensitive resin composition, comprising the steps of: applying the photosensitive resin composition according to any one of claims 1 to 25 or the resin composition according to claim 32 onto a substrate to form a photosensitive resin layer on the substrate;
(2) a step of exposing the photosensitive resin layer,
(3) developing the exposed photosensitive resin layer to form a relief pattern,
(4) a step of providing a relief pattern to a heat treatment to form a cured relief pattern
&Lt; / RTI &gt; A semiconductor device comprising a cured relief pattern obtained by the manufacturing method according to claim 33. The following ingredients:
(A) a polyimide precursor which is a polyamide acid, a polyamide acid ester, a polyamide acid salt, a polyamide acid amide, a polyhydroxyamide which may be a polyoxazole precursor, a polyaminoamide, a polyamide, a polyamideimide, At least one resin selected from the group consisting of polybenzoxazole, polybenzoxazole, polybenzimidazole, polybenzothiazole, and phenol resin,
Lt; / RTI &gt;
The crosslinking density is 1.0 × 10 ^-4 mol / cm 3 or more and 3.0 × 10 ^-3 mol / cm 3 or less,
5% weight reduction temperature is 250 占 폚 or higher and 400 占 폚 or lower,
Resin film. 36. The method of claim 35,
Wherein the crosslinking density is not less than 3.0 占^10-4 mol / cm3 and not more than ^2.010-3 mol / cm3. 37. The method of claim 35 or 36,
Wherein the component (A) is at least one selected from the group consisting of polyamide acid, polyamide acid ester, polyamide acid salt, polyamide acid amide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, And at least one resin selected from the group consisting of polybenzothiazoles. 37. A laminate according to any one of claims 35 to 37, wherein the resin film is laminated on a resin substrate having a glass transition temperature of 200 占 폚 or less. 37. A laminate according to any one of claims 35 to 37, wherein the resin film is laminated on a resin substrate having a glass transition temperature of 250 DEG C or less.

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