JP2017219850A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for producing a cured film having excellent adhesiveness to a polybenzoxazole resin, a Si substrate and a Cu substrate, having high resolution and heat resistance, and showing a normal tapered shape of a side face of an opening.SOLUTION: The photosensitive resin composition comprises: (A) at least one resin selected from the group consisting of polyamide acids as polyimide precursors, polyamide acid esters, polyamide acid salts, polyamide acid amides, polyhydroxyamides which can be polyoxazole precursors, polyaminoamides, polyamides, polyamideimides, polyimides, polybenzoxazoles, polybenzimidazoles, polybenzothiazoles and phenolic resins; (B) a photosensitive agent, and (C) at least one compound selected from the group consisting of polyfunctional (meth)acrylates and low molecular weight imide compounds having a molecular weight of less than 1000.SELECTED DRAWING: None

Description

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

  Conventionally, resins such as polyimide having excellent heat resistance, electrical characteristics, and mechanical characteristics have been used for insulating materials for electronic components and passivation films, surface protective films, interlayer insulating films, and the like for semiconductor devices. Among these resins such as polyimide, the resin provided in the form of a photosensitive polyimide precursor can be easily formed into a heat-resistant relief pattern film by thermal imidization treatment by applying the precursor, exposing, developing, and curing. Can be formed. The photosensitive polyimide precursor has a feature that the process can be greatly shortened as compared with the conventional non-photosensitive polyimide.

  On the other hand, in recent years, a method for mounting a semiconductor device on a printed wiring board has also changed from the viewpoint of improvement in integration degree and function, and reduction in chip size. A resin coating such as polyimide, such as BGA (Ball Griped Array) and CSP (Chip Size Packaging), which can be mounted at a higher density than conventional mounting methods using metal pins and lead-tin eutectic solder. A structure that directly contacts a solder bump has been used. When such a bump structure is formed, the film is required to have high heat resistance and chemical resistance. A method for improving the heat resistance of a polyimide coating or a polybenzoxazole coating by adding a thermal crosslinking agent to a composition containing a polyimide precursor or a polybenzoxazole precursor is disclosed (see Patent Document 1).

JP 2003-287889 A

  In the semiconductor device rewiring process, the interlayer insulation film forming process is performed separately by the former process manufacturer and the later process manufacturer, so that the resin such as polyimide is formed on the polybenzoxazole film formed in the previous process. The formation of these films is increasing. However, the conventional photosensitive resin composition has a problem in that when an additional film is formed on the polybenzoxazole film, the adhesiveness is insufficient, and thus peeling occurs after development and curing. Further, an adhesion assistant that improves the adhesion of the resin to the Si substrate and the Cu substrate has been conventionally known. However, when the adhesion assistant is used, there is a problem that the resolution or heat resistance of the relief pattern deteriorates.

  Furthermore, when forming the seed layer of the metal rewiring layer, it is necessary to sputter the metal on the surface of the resin without any gaps. For this purpose, it is desirable that the opening of the photosensitive resin pattern has a forward taper type whose side surface is gentler than the vertical to the bottom surface when patterning is completed, and preferably the taper angle is 80 ° or less. However, even when a conventional photosensitive resin composition is used, it is difficult to make the side surface of the opening portion into a forward taper type when patterning is completed.

  Therefore, the problem to be solved by the present invention is a cured film having excellent adhesion to a polybenzoxazole resin, a Si substrate and a Cu substrate, high resolution and heat resistance, and a side surface of the opening having a forward taper type. A photosensitive resin composition for producing a cured resin, a method for producing a cured relief pattern using the photosensitive resin composition, a semiconductor device provided with the cured relief pattern, and a resin film having excellent adhesion to a polybenzoxazole resin It is to provide a laminate that is laminated on a resin substrate having a glass transition temperature of 250 ° C. or lower.

The inventors of the present invention provide a photosensitive resin composition obtained by specifying any one of a resin structure, a type of initiator, and a type of coupler, which is in close contact with a polybenzoxazole resin, a Si substrate, and a Cu substrate. It provides excellent curing, high resolution and heat resistance, and gives a cured relief pattern that has a tapered front side, and contains a specific resin and has a specific crosslink density and a specific 5% weight reduction. The present inventors have found that a resin film having a temperature can be laminated on a resin substrate having a glass transition temperature of 250 ° C. or lower while being excellent in adhesiveness with a polybenzoxazole resin. That is, the present invention is as follows.
[1]
The following ingredients:
(A) Polyamide precursor polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole that can be a polyoxazole precursor At least one resin selected from the group consisting of polybenzothiazole, and phenolic resin;
(B) a photosensitive agent; and (C) at least one selected from the group consisting of a polyfunctional (meth) acrylate and a low molecular weight imide compound having a molecular weight of less than 1000;
A photosensitive resin composition comprising:
[2]
The component (A) is a polyimide precursor consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, and polybenzothiazole. The photosensitive resin composition according to [1], which is at least one selected resin.
[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]
The component (A) is represented by the following general formula (A1):
{Wherein, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, l is an integer of _{2 to} 150, and R ₁ and R ₂ are each independently A hydrogen atom or a monovalent organic group capable of radical polymerization. However, R ₁ and R ₂ are not simultaneously hydrogen atoms. }
And the component (C) is represented by the following general formula (C1):
{In the formula, R ₃ is a single bond, a hydrogen atom or a 1 to 3 valent organic group; R ₄ and R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 3 to 3 carbon atoms. 10 cycloalkyl groups, aryl groups, alkoxy groups or halogen atoms, and m is an integer of 1 or more. }
The photosensitive resin composition of any one of [1]-[3] containing the maleimide represented by these.
[5]
The component (A) is represented by the following general formula (A2):
{Wherein X ₂ is a tetravalent organic group, Y ² is a divalent organic group, n is an integer of 2 to 150, and R ₆ and R ₇ are each independently A hydrogen atom, the following general formula (A3):
_(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. However, R ₆ and R ₇ are not both hydrogen atoms at the same time. }
The photosensitive resin composition of any one of [1]-[4] which is a polyimide precursor represented by these.
[6]
The component (C) is represented by the following general formula (C2):
{In the formula, R ₁₁ represents a single bond, a hydrogen atom, or a 1-3 valent organic group; R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 3 to 3 carbon atoms. 10 cycloalkyl groups, aryl groups, alkoxy groups or halogen atoms, and q is an integer of 2-4. }
The photosensitive resin composition of any one of [1]-[5] containing the maleimide represented by these.
[7]
The photosensitive resin composition according to any one of [1] to [6], wherein the component (B) is an oxime photopolymerization initiator.
[8]
The component (B) is the following components (B1) and (B2):
(B1) an oxime ester compound in which the 0.001 wt% solution has an i-ray absorbance of 0.15 to 0.5, and the 0.001 wt% solution has a g-ray absorbance and an h-ray absorbance of 0.2 or less; and (B2) An oxime ester compound in which the i-line absorbance of the 0.001 wt% solution is 0.1 or less and the g-ray absorbance or h-ray absorbance of the 0.001 wt% solution is 0.05 or more;
The photosensitive resin composition of any one of [1]-[7] containing at least 1 sort (s) selected from the group which consists of.
[9]
The photosensitive resin composition according to [8], wherein an i-line absorbance of a 0.001 wt% solution of the component (B1) is 0.15 to 0.35.
[10]
The component (B1) is represented by the following general formulas (B11) and (B12):
{Wherein R ₁₄ is a C _{1 to} C ₁₀ fluorine-containing alkyl group, and R ₁₅ , R ₁₆ , and R ₁₇ are each independently a C _{1 to} C ₂₀ alkyl group, or a C _{3 to} C ₂₀ cycloalkyl _group, an aryl group of C 6 _{-C 20,} or an alkoxy group of _C 1 _{-C 20,} and r is an integer from 0 to 5. }
{In the formula, R ₁₈ is a C _{1 to} C ₃₀ divalent organic group, and R _{19 to} R ₂₆ are each independently a C _{1 to} C ₂₀ alkyl group or a C _{3 to} C ₂₀ cycloalkyl group. , an aryl group of _C 6 _{-C 20,} or an alkoxy group of _C 1 _{-C 20,} and s is an integer of 0 to 3. }
The photosensitive resin composition as described in [8] or [9] containing at least 1 sort (s) selected from the group which consists of oxime ester compound represented by these.
[11]
In addition to the above components (A) to (C),
(D) The following general formula (D1):
{Wherein R ₂₇ and R ₂₈ are C _{1 to} C ₄ alkyl groups, R ₂₉ is a C _{1 to} C ₆ divalent organic group, and R ₃₀ is composed of nitrogen, oxygen, and sulfur. An organic group of C _{1 to} C ₂₀ bonded to a carbonyl group by an atom selected from the group, t is an integer selected from 1, 2, and 3, and u is an integer selected from 0, 1, and 2. And t and u satisfy the relationship t + u = 3. }
The photosensitive resin composition of any one of [1]-[10] containing the silicon containing compound represented by these.
[12]
As the component (D), in addition to the silicon-containing compound represented by the formula (D1), the following general formula (D2):
{Wherein R ₃₁ and R ₃₂ are C _{1 to} C ₄ alkyl groups, R ₃₃ is a C _{1 to} C ₆ divalent organic group, and v is an integer selected from 1, 2, and 3 And w is an integer selected from 0, 1, and 2, and v and w satisfy the relationship of v + w = 3. }
The photosensitive resin composition according to [11], further comprising a silicon-containing compound represented by:
[13]
In addition to the above components (A) to (C),
(E) The following general formula (E1):
{Wherein R ₃₄ is a C _{1 to} C ₂₀ organic group or silicon-containing organic group, and R ₃₅ is a C _{1 to} C ₂₀ bonded to a thiocarbonyl group by an atom selected from the group consisting of nitrogen, oxygen, and sulfur. Is an organic group. }
The photosensitive resin composition of any one of [1]-[10] containing the sulfur containing compound represented by these.
[14]
For 100 parts by mass of component (A),
0.1 to 20 parts by mass of the component (B); and 1 to 40 parts by mass of the component (C);
The photosensitive resin composition of any one of [1]-[10] containing.
[15]
For 100 parts by mass of component (A),
0.1 to 20 parts by mass of the component (B); and 10 to 35 parts by mass of the component (C);
The photosensitive resin composition of any one of [1]-[10] containing.
[16]
For 100 parts by mass of component (A),
0.1-20 parts by mass of the component (B);
1 to 40 parts by mass of the (C) component; and 0.1 to 20 parts by mass of the (D) component;
The photosensitive resin composition as described in [11] or [12].
[17]
For 100 parts by mass of component (A),
0.1-20 parts by mass of the component (B);
10 to 35 parts by mass of the component (C); and 0.1 to 20 parts by mass of the component (D);
The photosensitive resin composition as described in [11] or [12].
[18]
For 100 parts by mass of component (A),
0.1-20 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], comprising:
[19]
For 100 parts by mass of component (A),
0.1-20 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], comprising:
[20]
The following ingredients:
(AX) a photosensitive polyimide precursor;
The following (B1) and (B2) components:
(B1) an oxime ester compound in which the 0.001 wt% solution has an i-line absorbance of 0.15 to 0.5, and the 0.001 wt% solution has a g-line absorbance and an h-line absorbance of 0.2 or less, and (B2) An oxime ester compound in which the 0.001 wt% solution has an i-line absorbance of 0.1 or less and the 0.001 wt% solution has a g-line absorbance or h-line absorbance of 0.05 or more,
At least one selected from the group consisting of:
A photosensitive resin composition comprising:
[21]
The (AX) component is represented by the following general formula (A2):
{Wherein X ₂ is a tetravalent organic group, Y ² is a divalent organic group, n is an integer of 2 to 150, and R ₆ and R ₇ are each independently A hydrogen atom, the following general formula (A3):
_(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. However, R ₆ and R ₇ are not both hydrogen atoms at the same time. }
The photosensitive resin composition as described in [20] which is the polyimide precursor represented by these.
[22]
The photosensitive resin composition according to [20] or [21], wherein an i-ray absorbance of a 0.001 wt% solution of the component (B1) is 0.15 to 0.35.
[23]
The component (B1) is represented by the following general formulas (B11) and (B12):
{Wherein R ₁₄ is a C _{1 to} C ₁₀ fluorine-containing alkyl group, and R ₁₅ , R ₁₆ , and R ₁₇ are each independently a C _{1 to} C ₂₀ alkyl group, or a C _{3 to} C ₂₀ cycloalkyl _group, an aryl group of C 6 _{-C 20,} or an alkoxy group of _C 1 _{-C 20,} and r is an integer from 0 to 5. }
{In the formula, R ₁₈ is a C _{1 to} C ₃₀ divalent organic group, and R _{19 to} R ₂₆ are each independently a C _{1 to} C ₂₀ alkyl group or a C _{3 to} C ₂₀ cycloalkyl group. , an aryl group of _C 6 _{-C 20,} or an alkoxy group of _C 1 _{-C 20,} and s is an integer of 0 to 3. }
The photosensitive resin composition of any one of [20]-[22] containing at least 1 sort (s) selected from the group which consists of oxime ester compound represented by these.
[24]
The total content of the component (B1) and the component (B2) with respect to 100 parts by mass of the (AX) component is 0.1 to 10 parts by mass, according to any one of [20] to [23]. Photosensitive resin composition.
[25]
The photosensitive composition according to any one of [20] to [24], wherein the total content of the component (B1) and the component (B2) with respect to 100 parts by mass of the (AX) component is 0.5 to 5 parts by mass. Resin composition.
[26]
The following ingredients:
(AY) polyimide precursor; and (D) the following general formula (D1):
{Wherein R ₂₇ and R ₂₈ are C _{1 to} C ₄ alkyl groups, R ₂₉ is a C _{1 to} C ₆ divalent organic group, and R ₃₀ is composed of nitrogen, oxygen, and sulfur. An organic group of C _{1 to} C ₂₀ bonded to a carbonyl group by an atom selected from the group, t is an integer selected from 1, 2, and 3, and u is an integer selected from 0, 1, and 2. And t and u satisfy the relationship t + u = 3. }
A silicon-containing compound represented by:
A resin composition comprising:
[27]
As the component (D), in addition to the silicon-containing compound represented by the formula (D1), the following general formula (D2):
{Wherein R ₃₁ and R ₃₂ are C _{1 to} C ₄ alkyl groups, R ₃₃ is a C _{1 to} C ₆ divalent organic group, and v is an integer selected from 1, 2, and 3 And w is an integer selected from 0, 1, and 2, and v and w satisfy the relationship of v + w = 3. }
The resin composition according to [26], further comprising a silicon-containing compound represented by:
[28]
The following ingredients:
(AY) polyimide precursor; and (E) the following general formula (E1):
{Wherein R ₃₄ is a C _{1 to} C ₂₀ organic group or silicon-containing organic group, and R ₃₅ is a C ₁ to C bonded to a thiocarbonyl group by an atom selected from the group consisting of nitrogen, oxygen, and sulfur. ₂₀ organic groups. }
A sulfur-containing compound represented by:
A resin composition comprising:
[29]
The component (AY) is represented by the following general formula (A2):
{Wherein X ₂ is a tetravalent organic group, Y ² is a divalent organic group, n is an integer of 2 to 150, and R ₆ and R ₇ are each independently A hydrogen atom, the following general formula (A3):
_(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. However, R ₆ and R ₇ are not both hydrogen atoms at the same time. }
The resin composition according to any one of [26] to [28], which is a polyimide precursor represented by:
[30]
For 100 parts by mass of the (AY) component,
0.1 to 20 parts by mass of the component (D1); and 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], comprising 0.1 to 20 parts by mass of the component (E) with respect to 100 parts by mass of the component (AY).
[32]
(B) The resin composition according to any one of [26] to [31], further containing a photosensitizer.
[33]
below:
(1) The photosensitive resin composition according to any one of [1] to [25] or the resin composition according to [32] is applied on a substrate, and the photosensitive resin layer is formed on the substrate. Forming, and
(2) exposing the photosensitive resin layer;
(3) developing the photosensitive resin layer after the exposure to form a relief pattern;
(4) subjecting the relief pattern to a heat treatment to form a cured relief pattern;
A method for producing a cured relief pattern.
[34]
A semiconductor device provided with the hardening relief pattern obtained by the manufacturing method as described in [33].
[35]
The following ingredients:
(A) Polyamide precursor polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole that can be a polyoxazole precursor At least one resin selected from the group consisting of polybenzothiazole, and phenolic resin,
Including
Crosslink density is 1.0 × 10 ⁻⁴ mol / cm ³ or more, 3.0 × 10 ⁻³ mol / cm ³ or less, and 5% weight loss temperature is 250 ° C. or more and 400 ° C. or less.
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]
The component (A) is a polyimide precursor consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, and polybenzothiazole. The resin film according to [35] or [36], which is at least one selected resin.
[38]
[35] to [37] A laminate in which the resin film according to any one of [37] to [37] is laminated on a resin substrate having a glass transition temperature of 200 ° C. or lower.
[39]
[35] to [37] A laminate in which the resin film according to any one of [37] to [37] is laminated on a resin substrate having a glass transition temperature of 250 ° C. or lower.

  According to the present invention, a photosensitive film for producing a cured film having excellent adhesion to a polybenzoxazole resin, a Si substrate, and a Cu substrate, high resolution and heat resistance, and a side surface of an opening having a forward taper type. Resin composition, method for producing a cured relief pattern using the photosensitive resin composition, a semiconductor device provided with the cured relief pattern, a resin film having excellent adhesion to a polybenzoxazole resin, and the resin film having a glass transition Provided is a laminate laminated on a resin substrate having a temperature of 250 ° C. or lower.

It is the schematic which shows 1 process of the evaluation method of a taper angle. It is the schematic which shows 1 process of the evaluation method of a taper angle. It is the schematic which shows 1 process of the evaluation method of a taper angle. It is the schematic which shows 1 process of the evaluation method of a taper angle. It is the schematic which shows 1 process of the evaluation method of a taper angle.

  The present invention will be specifically described below. Throughout the present specification, when a plurality of structures represented by the same symbol in the general formula are present in a molecule, they may be the same as or different from each other.

<Resin composition>
(A) Polyamide precursor polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole that can be a polyoxazole precursor At least one resin selected from the group consisting of polybenzothiazole, and phenolic resin;
(B) a photosensitive agent; and (C) at least one selected from the group consisting of a polyfunctional (meth) acrylate and a low molecular weight imide compound having a molecular weight of less than 1000;
The resin composition containing is described.

(A) component (A) component used in this composition is polyhydroxyamide, polyaminoamide which can be a polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyoxazole precursor which is a polyimide precursor, It is 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 a polybenzoxazole resin, a group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, polybenzothiazole At least one resin selected from the above is preferred.

  The weight average molecular weight of these resins is preferably 1,000 or more and more preferably 5,000 or more in terms of polystyrene by gel permeation chromatography from the viewpoint 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 as 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 and causes development by dissolution or non-dissolution in a subsequent development step when used together with the later-described (B) photosensitive agent.

  Photosensitive resins include polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyamide, polyamidoimide, polyimide, polybenzoxazole, polybenzimidazole, and polybenzthiazole, which are polyimide precursors, after heat treatment. From the viewpoint that these resins are excellent in heat resistance and mechanical properties, polyimide precursors, polyamides, and / or polyimides are preferably used. These photosensitive resins should be selected according to the desired application from the viewpoint of whether to prepare a negative type or a positive type photosensitive resin composition together with the photosensitive agent (B) described later. Can do.

[Polyimide precursor]
In the resin composition of the present invention, from the viewpoint of heat resistance and photosensitivity, one of (A) resin, (AX) photosensitive polyimide precursor, and (AY) polyimide precursor is preferably represented by the following general formula (A1). ):
{Wherein, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, l is an integer of _{2 to} 150, and R ₁ and R ₂ are each independently A hydrogen atom or a monovalent organic group capable of radical polymerization. However, R ₁ and R ₂ are not simultaneously hydrogen atoms. }
More preferably, the polyamide has a structure represented by the following general formula (A2):
{Wherein X ₂ is a tetravalent organic group, Y ² is a divalent organic group, n is an integer of 2 to 150, and R ₆ and R ₇ are each independently A hydrogen atom, the following general formula (A3):
_(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. However, R ₆ and R ₇ are not both hydrogen atoms at the same time. }
Is a polyamide having a structure represented by
(A) Resin, (AX) photosensitive polyimide precursor, or (AY) polyimide precursor is converted into polyimide by heating (for example, 180 ° C. or more) cyclization treatment.

In the general formula (A2), the tetravalent organic group represented by X ₂ is preferably an organic group having 6 to 40 carbon atoms, more preferably a —COOR ₆ group, from the viewpoints of heat resistance and photosensitive properties. And -COOR ₇ group and -CONH- group are each an aromatic group or an alicyclic aliphatic group in the ortho position. The tetravalent organic group represented by X ₂ is more preferably the following formula:
Although the structure represented by these is mentioned, it is not limited to these. Structure of X ₂ may be two or more kinds in combination.

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 viewpoint of heat resistance and photosensitive properties.
{In the formula, 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 ). }
Although the structure represented by these is mentioned, it is not limited to these. The structure of Y ² may be two or more kinds in combination.

Regarding R ₆ and R ₇ , R ₈ in the general formula (A3) is preferably a hydrogen atom or a methyl group, and R ₉ and R ₁₀ are preferably a hydrogen atom from the viewpoint of photosensitive properties. Further, p is preferably an integer of 2 to 10, more preferably an integer of 2 to 4, from the viewpoint of photosensitive characteristics.

  As a method of imparting photosensitivity to the photosensitive resin composition when using a polyimide precursor as the resin of the component (A) and when using the (AX) photosensitive polyimide precursor or the (AY) polyimide precursor, Examples include an ester bond type and an ion bond type. The former is a method of introducing a photopolymerizable group, that is, a compound having an olefinic double bond, into the side chain of the polyimide precursor by an ester bond, and the latter has a carboxyl group and an amino group of the polyimide precursor ( In this method, a photopolymerizable group is imparted by bonding an amino group of a (meth) acrylic compound via an ionic bond.

[Preparation method of polyimide precursor]
The polyimide precursor of the ester-linked, firstly, a tetracarboxylic acid dianhydride containing tetravalent organic group X ₂ described above, the photopolymerizable alcohols and optionally saturated aliphatic alcohols having an unsaturated double bond And a partially esterified tetracarboxylic acid (hereinafter also referred to as an acid / ester), and this and a diamine containing the divalent organic group Y ₂ described above. Obtained by polycondensation.

(Preparation of acid / ester)
Examples of the tetracarboxylic dianhydride containing a tetravalent organic group X ₂ that are preferably used for preparing an ester bond type polyimide precursor include pyromellitic anhydride, diphenyl ether-3,3 ′, 4. , 4′-tetracarboxylic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic dianhydride, biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, diphenyl Sulfone-3,3 ′, 4,4′-tetracarboxylic dianhydride, diphenylmethane-3,3 ′, 4,4′-tetracarboxylic dianhydride, 2,2-bis (3,4-phthalic anhydride) Acid) propane, 2,2-bis (3,4-phthalic anhydride) -1,1,1,3,3,3-hexafluoropropane and the like, but are not limited thereto. . These can be used alone or as a mixture of two or more.

  Examples of alcohols having a photopolymerizable unsaturated double bond that are suitably used for preparing an ester-linked polyimide precursor include 2-acryloyloxyethyl alcohol and 1-acryloyloxy-3-propyl. Alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2 -Hydroxy-3-butoxypropyl acrylate, 2-hydroxy-3-t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2-methacryloyloxyethyl alcohol 1-methacryloyloxy-3-propyl alcohol, 2-methacrylamidoethyl alcohol, 2-hydroxy-3-methoxypropyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2- Examples thereof include hydroxy-3-butoxypropyl methacrylate, 2-hydroxy-3-t-butoxypropyl methacrylate, 2-hydroxy-3-cyclohexyloxypropyl methacrylate and the like.

  For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and the like are mixed as a saturated aliphatic alcohol having 1 to 4 carbon atoms with alcohol having a photopolymerizable unsaturated double bond. Can also be used.

  The preferable tetracarboxylic dianhydride described above and the preferable alcohol described above are mixed in a suitable reaction solvent at a temperature of 20 to 50 ° C. for 4 to 10 hours in the presence of a basic catalyst such as pyridine. By stirring, dissolving, and mixing, the esterification reaction of the acid anhydride proceeds, and the desired acid / ester body can be obtained.

  As a reaction solvent, a solvent that completely dissolves an acid / ester and a polyimide precursor that is an amide polycondensation product of this with a diamine component, for example, N-methyl-2-pyrrolidone, N, N- Examples thereof include dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, and γ-butyrolactone.

  Other reaction solvents include ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, etc., for example, 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-dichlorobenzene, hexane, heptane, benzene, toluene, xylene, etc. Can be mentioned. These may be used alone or in combination of two or more as required.

(Preparation of polyimide precursor)
To an acid / ester (typically, a solution in a reaction solvent) under ice cooling, a suitable dehydration condensing agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1 , 1-carbonyldioxy-di-1,2,3-benzotriazole, N, N′-disuccinimidyl carbonate and the like are added and mixed to convert the acid / ester into a polyanhydride. Thereafter, the preferred divalent diamines containing organic group Y ₁ was allowed to separate dissolved or dispersed in a solvent solution or dispersion was added dropwise to polyanhydrides, by engaged amide polycondensation, the photosensitive resin of interest Can be obtained.

Preferred diamines containing a divalent organic group Y ₁ include, for example, p-phenylene diamine, m-phenylene diamine, 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′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 3,3′- Diaminodiphenyl sulfone, 4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,3′-diamino Benzophenone, 4,4'-diaminodiphenylmethane, 3,4 '-Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) Benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4-bis (4-aminophenoxy) biphenyl, 4,4-bis (3 -Aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenyl) benzene, 1,3 -Bis (4-aminophenyl) benzene, 9,10-bis (4-aminophenyl) anthracene, 2,2-bis ( -Aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl) propane, 2,2-bis [4- (4- Aminophenoxy) phenyl) hexafluoropropane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, ortho-tolidine sulfone, 9,9-bis (4-aminophenyl) fluorene; on the benzene ring of these diamines A compound in which part of the hydrogen atom 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 ′ -Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl -4,4'-diaminodiphenylmethane, 3,3'-dimethyloxy-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl; and mixtures thereof. It is not limited to.

  Furthermore, in order to improve the adhesiveness between the photosensitive resin layer formed on the substrate and various substrates by applying the photosensitive resin composition of the present invention on the substrate, a polyimide precursor is used as the resin of component (A). And (AX) photosensitive polyimide precursor or (AY) polyimide precursor, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (3- It is also possible to copolymerize diaminosiloxanes such as (aminopropyl) tetraphenyldisiloxane.

  After completion of the amide polycondensation reaction, the water-absorbing by-product of the dehydrating condensing agent coexisting in the reaction solution is filtered off if necessary, and then a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof is removed The polymer component is added to the polymer component, and the polymer component is precipitated. Further, the polymer is purified by repeating redissolution, reprecipitation and the like, and vacuum drying is performed to obtain the target polyimide precursor. Isolate. In order to improve the degree of purification, the polymer solution may be passed through a column packed with an anion and / or cation exchange resin swollen with a suitable organic solvent to remove ionic impurities.

  The weight average molecular weight of the ester bond type polyimide precursor is preferably 8,000 to 150,000, and 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, and when it is 150,000 or less, the dispersibility in the developer is good and the resolution performance of the relief pattern is good. Tetrahydrofuran and / or N-methyl-2-pyrrolidone is recommended as a developing solvent for gel permeation chromatography. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is preferable to select an organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.

(B) Photosensitizer (B) As the photosensitizer, a compound conventionally used as a photopolymerization initiator for UV curing can be arbitrarily selected. (B) Examples of compounds that can be suitably used as a photosensitizer include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, and fluorenone; Acetophenone derivatives such as diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone; benzil Benzyl derivatives such as benzyldimethyl ketal and benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin and benzoin methyl ether; 1-phenyl-1,2-butanedione 2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) ) Oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione Oximes such as -2- (o-benzoyl) oxime; N-aryl glycines such as N-phenylglycine; peroxides such as benzoyl perchloride; aromatic biimidazoles and the like. Is not to be done. Moreover, you may use these 1 type or a 2 or more types of mixture. Among these, oximes are more preferable particularly from the viewpoint of photosensitivity.

(B) The oximes used as photosensitizers are the following components (B1) and (B2):
(B1) an oxime ester compound having a g-line absorbance and h-line absorbance of 0.2 or less and an i-line absorbance of 0.15 to 0.5 with respect to a 0.001 wt% solution; and (B2) 0.001 wt An oxime ester compound having a g-line absorbance or h-line absorbance of 0.05 or more and an i-line absorbance of 0.1 or less with respect to a% solution;
It is preferably at least one 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% and using a 1 cm quartz cell and a normal spectrophotometer.

  Preferred compounds as the component (B1) include, for example, Irgacure OXE03 (trade name, manufactured by BASF), Adekaoptomer NCI831 (trade name, manufactured by ADEKA), TR-PBG326 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd., trade name) ), HTPI 426 (manufactured by Heraeus, trade name), HTPI 428 (manufactured by Heraeus, trade name), or a mixture thereof.

  As a component (B1), when a compound having an i-ray absorbance of less than 0.15 in a 0.001 wt% solution is used, the absorbance is not sufficient, so that a large amount of initiator needs to be added for curing. In that case, since it becomes difficult to be influenced by oxygen inhibition on the surface of the coating film, the degree of surface hardening increases, and the opening after exposure and development does not become a forward tapered shape. Even when the i-ray absorbance exceeds 0.5, or when at least one of the g-ray absorbance and the h-ray absorbance exceeds 0.2, the absorbance is too high and surface hardening tends to proceed. The part does not have a forward tapered shape.

  More preferable component (B1) is an oxime ester compound having an i-line absorbance of 0.15 to 0.35 in a 0.001 wt% solution, and more preferable components (B1) are the following general formulas (B11) and (B12). :

{Wherein R ₁₄ is a C _{1 to} C ₁₀ fluorine-containing alkyl group, and R ₁₅ , R ₁₆ , and R ₁₇ are each independently a C _{1 to} C ₂₀ alkyl group, or a C _{3 to} C ₂₀ cycloalkyl _group, an aryl group of C 6 _{-C 20,} or an alkoxy group of _C 1 _{-C 20,} and r is an integer from 0 to 5. }

{In the formula, R ₁₈ is a C _{1 to} C ₃₀ divalent organic group, and R _{19 to} R ₂₆ are each independently a C _{1 to} C ₂₀ alkyl group or a C _{3 to} C ₂₀ cycloalkyl group. , an aryl group of _C 6 _{-C 20,} or an alkoxy group of _C 1 _{-C 20,} and s is an integer of 0 to 3. }
Is at least one selected from the group consisting of oxime ester compounds represented by:

In the photosensitive resin composition of the present invention, the oxime ester compound (B2) also functions as a photopolymerization initiator.
The absorbance of the oxime ester compound (B2) can be measured in the same manner as in the case of the oxime ester compound (B1).

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

  As a component (B2), when a compound having a g-ray absorbance and h-ray absorbance of less than 0.05 is used as a 0.001 wt% solution, the absorbance is not sufficient, so that a large amount of initiator needs to be added for curing. . In that case, since it becomes difficult to be influenced by oxygen inhibition on the surface of the coating film, the degree of surface hardening increases, and the opening after exposure and development does not become a forward tapered shape. Even in the case where the i-line absorbance exceeds 0.1, the absorbance is too high and surface hardening is likely to proceed, and the opening after exposure and development does not have a forward tapered shape.

  The total amount of the (B1) component and the (B2) component with respect to 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor is in the range of 0.1 to 20 parts by mass. It is preferable that the range is 0.5 to 5 parts by mass. The total amount of the (B1) component and the (B2) component is 0.1 parts by mass or more with respect to 100 parts by mass of the (A) resin, the (AX) photosensitive polyimide precursor, or the (AY) polyimide precursor. When it is excellent in photosensitivity and is 20 parts by mass or less, the forward taper property is excellent.

(C) At least one selected from the group consisting of a polyfunctional (meth) acrylate and a low molecular weight imide compound having a molecular weight of less than 1000. The component (C) comprises a polyfunctional (meth) acrylate and a low molecular weight imide compound having a molecular weight of less than 1000. It is at least one selected from the group. “(Meth) acrylate” means acrylate or methacrylate. 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.

  As polyfunctional (meth) acrylate, isocyanuric acid tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate And dipentaerythritol hexa (meth) acrylate.

The low molecular weight imide compound having a molecular weight of less than 1000 is represented by the following general formula (C1):
{In the formula, R ₃ is a single bond, a hydrogen atom or a 1 to 3 valent organic group; R ₄ and R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 3 to 3 carbon atoms. 10 cycloalkyl groups, aryl groups, alkoxy groups or halogen atoms, and m is an integer of 1 or more. }
It is preferable that it is maleimide represented by these.
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 1000 is represented by the following general formula (C2):
{In the formula, R ₁₁ represents a single bond, a hydrogen atom, or a 1-3 valent organic group; R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 3 to 3 carbon atoms. 10 cycloalkyl groups, aryl groups, alkoxy groups or halogen atoms, and q is an integer of 2-4. }
It is more preferable that it is maleimide represented by these.

  By using a low molecular weight imide compound as the component (C), a cured film having excellent adhesion after development on a polybenzoxazole resin can be obtained. Although the mechanism by which the relief pattern on the polybenzoxazole resin is excellent in adhesion after development is not clear, in the heating step (about 100 ° C.) for drying the solvent when forming the coating film of the relief pattern, as the component (C) The low molecular weight imide compound and the polybenzoxazole resin are stacked and interact at the resin interface, so that the developer soaks into the interface between the coating film and the polybenzoxazole resin during development, or solvates. It is inferred that dissolution is suppressed and as a result, peeling of the relief pattern is suppressed.

  (C) Specific examples of the low molecular weight imide compound include 1-phenylpyrrolidine-2,5-dione, succinimide, N-pentylsuccinimide, glutadine, 2,6 (1H, 3H) -pyridinedione, N-ethylmaleimide, Fluorimide, N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (2-chlorophenyl) maleimide, N- (4-methylphenyl) maleimide, N- (4-ethoxyphenyl) maleimide, N -Isopropylmaleimide, N-methylmaleimide, N- (2-nitrophenyl) maleimide, N- (2-methylphenyl) maleimide, 1- (2,4-dimethylphenyl) -3-pyrroline-2, 5-dione, 1- (1,1′-biphenyl-4-yl) -1H-pyro 2,5-dione, N-cyclohexylmaleimide, N-butylmaleimide, 1- (hydroxymethyl) -1H-pyrrole-2,5-dione, 3-methyl-4-vinyl-1H-pyrrole-2 , 5-dione, N- (4-aminophenyl) maleimide, 3,4-dibromo-3-pyrroline-2,5-dione, N-benzylmaleimide, 6,7-methylenedioxy-4-methyl- 3-maleimidocoumarin, maleimide, 2,3-dichloromaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-acetylphenyl) maleimide, N-propylmaleimide, N- (1-pyrenyl) Maleimide, N- (4-methoxyphenyl) maleimide, N- (fluoranthen-3-yl) maleimide, -(4-vinylphenyl) maleimide, N- (m-vinylphenyl) maleimide, 4-[(2,5-dioxo-1-pyrrolyl) methyl] cyclohexanecarboxylate succinimidyl, eosin-5-maleimide, squalenemaleimide, N- (2,4,6-tribromophenyl) maleimide, benzophenone-4-maleimide, maleimide nitroxide, N- (3-nitrophenyl) maleimide, N- (4-nitrophenyl) maleimide, 2,5 -Dioxo-3-pyrroline-1-hexanoic acid, 3- (N-maleimidylpropionyl) biocytin, N- (2,4-dinitroanilino) maleimide, coumarin maleimide, N- (4-bromophenyl) maleimide, N-isobutylmaleimide, N-tert-butylmale Inimide, N-octylmaleimide, N-decylmaleimide, N-bromomethylmaleimide, N-cyanomethylmaleimide, N-ethoxymethylmaleimide, N-3-nitro-4-methylbenzylmaleimide, N-aryloxymethylmaleimide N-aminomethylmaleimide, N-diethylaminomethylmaleimide, N-dibutylaminomethylmaleimide, N- (1-piperidinomethyl) maleimide, N- (1-morpholinomethyl) maleimide, N-anilinomethylmaleimide, N- (2 -Ethoxyethyl) maleimide, 2- (2,5-dioxo-3-pyrrolin-1-yl) ethyl propionate, N- (2,2,2-trifluoroethyl) maleimide, N- (methylmaleoylethyl) Maleimide, N- (3-acetoxypro M) maleimide, 1- (2-hydroxypropyl) -1H-pyrrole-2,5-dione, N-methoxymaleimide, N-acetyloxymaleimide, N-benzyloxymaleimide, N-benzenesulfonyloxymaleimide, N- (Dimethylamino) maleimide, N-acetylaminomaleimide, N- (1-morpholino) maleimide, N- (phenylsulfonyl) maleimide, N-anilinomaleimide, N, N ′-(1,2-phenylene) bis ( Maleimide), N, N ′-(1,3-phenylene) bis (maleimide), N, N′-ethylenebis (maleimide), 1,6-bismaleimide hexane, N-dodecylmaleimide, N— (2-methoxyphenyl) maleimide, N- (chloromethyl) maleimide N, N ′-(4-methyl-1,3-phenylene) bis (maleimide), 4,4′-bismaleimide diphenylmethane, N, N ′-(1,4-phenylene) bis (maleimide), polyphenylene Methanemaleimide, N, N ′-[sulfonylbis (4,1-phenylene)] bis (maleimide), N- [4- (phenylazo) phenyl] 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 (1H-pyrrole) -2,5-dione), N, N '-[(1,3-phenylene) bisoxybis (3,1-phenylene)] bis (maleimide), N- (4-maleimidobutyryloxy) ) Succinimide, N- (8-maleimidocapryloxy) succinimide, 4-[(2,5-dioxo-1-pyrrolyl) methyl] cyclohexane-1-carboxylic acid 3-sulfosuccinimidyl, 2,2 ′, 3 , 3′-tetraphenyl-N, N′-ethylene dimaleimide, fluorescein maleimide, N, N ′, N ″-[nitrilotris (ethylene)] tris (maleimide), and the like.

  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. Among low molecular weight imide compounds having an unsaturated bond in the cyclic structure, as represented by the general formula (C1) or (C2), it has a maleimide structure that is planar and easily sterically stacks with benzoxazole. The compound is more preferable from the viewpoint of adhesion after development on the polybenzoxazole resin.

  Furthermore, among the compounds having a maleimide structure, a divalent maleimide is more preferable than a monovalent maleimide from the viewpoint that it is difficult to dissolve in a developer due to a crosslinking reaction. In addition, divalent maleimides have less steric hindrance than trivalent maleimides and are easier to stack with polybenzoxazoles. Therefore, bismaleimide is more preferable from the viewpoint of adhesion with the polybenzoxazole resin. Among them, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, 4,4′-bismaleimide diphenylmethane, or polyphenylenemethanemaleimide suppresses shrinkage during curing of the photosensitive resin composition, and is a polyimide. Or from a viewpoint of improving adhesiveness with a polybenzoxazole resin, it is still more preferable.

  (C) The compounding quantity of a component is 1-40 mass parts when the photosensitive resin composition contains 100 mass parts of resin of (A) component, and (B) component 0.1-20 mass parts, Preferably it is 10-35 mass parts. When the blending amount of the component (C) is less than 1 part by mass, the adhesion is insufficient, and when it exceeds 40 parts by mass, the cured relief pattern obtained from the composition becomes brittle, and a passivation film and a buffer coat film. It is not suitable for applications such as interlayer insulation films.

(D) Silicon-containing compound (D) The component is represented by the following general formula (D1):
{Wherein R ₂₇ and R ₂₈ are C _{1 to} C ₄ alkyl groups, R ₂₉ is a C _{1 to} C ₆ divalent organic group, and R ₃₀ is selected from nitrogen, oxygen, and sulfur. An organic group of C _{1 to} C ₂₀ bonded to a 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 satisfy the relationship t + u = 3. }
It is a silicon containing compound represented by these.

As R ₃₀ , specifically,
Methylamino group, ethylamino group, n-propylamino group, n-butylamino group, n-hexylamino group, n-octylamino group, isopropylamino group, isobutylamino group, t-butylamino group, isoamylamino group, Mono- and dialamino groups such as cyclopentyl group, cyclohexylamino group, dimethylamino group, diethylamino group, dibutylamino group, dicyclohexylamino group;
Aromatic ring-containing amino groups such as phenylamino group, benzylamino group, diphenylamino group;
Heterocyclic-containing amino groups such as picolyl group, aminotriazyl group, furfurylamino group, morpholino group;
Alkoxy groups such as methoxy group, ethoxy group, n-butoxy group, t-butoxy group, hexyloxy group, cyclohexyloxy group;
Alkylaryloxy groups or arylalkyloxy groups such as phenoxy group, benzyloxy group, tolyloxy group;
A heterocyclic ring-containing alkoxy group such as a furfurylalkoxy group and a 2-pyridinylethoxy group;
Alkylthio groups such as methylthio group, ethylthio group, n-butylthio group, t-butylthio group, hexylthio group, cyclohexylthio group or phenylthio group;
These mixtures, etc. are mentioned.

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

  The compounding quantity of the silicon-containing compound represented by the formula (D1) is 0.1 to 20 parts by mass with respect to 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor. It is preferable that it is 0.5-10 mass parts from a viewpoint of improving heat resistance and adhesiveness. By blending the silicon-containing compound represented by the formula (D1) with 0.1 part by mass or more with respect to 100 parts by mass of the (A) resin, the (AX) photosensitive polyimide precursor, or the (AY) polyimide precursor, it is excellent. Adhesion is ensured, and excellent heat resistance is maintained by blending at 20 parts by mass or less.

In addition to the silicon-containing compound represented by the formula (D1) as the component (D), the following general formula (D2):
{Wherein R ₃₁ and R ₃₂ are C _{1 to} C ₄ alkyl groups, R ₃₃ is a C _{1 to} C ₆ divalent organic group, and v is an integer selected from 1, 2, and 3 And w is an integer selected from 0, 1, and 2, and v and w satisfy the relationship of v + w = 3. }
It is preferable to further add a silicon-containing compound represented by the formula (1) to the photosensitive resin composition.

  Examples of the silicon-containing compound represented by the formula (D2) include 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropylethoxydimethoxysilane, 3-ureidopropyldiethoxymethoxysilane, 3 -Ureidopropylmethyldiethoxysilane, 3-ureidopropylmethyldimethoxysilane, 3-ureidopropylethyldiethoxysilane, 3-ureidopropylethyldimethoxysilane, 3-ureidopropyldimethylethoxysilane, 3-ureidopropyldimethylmethoxysilane, etc. And mixtures thereof.

  The compounding amount of the silicon-containing compound represented by the formula (D2) is 0.1 to 20 parts by mass with respect to 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor. It is preferable that it is 0.5-10 mass parts from a viewpoint of improving heat resistance and adhesiveness. When preparing the resin composition of the present invention as a photosensitive resin composition, in addition to the silicon-containing compound represented by the formula (D1), a silicon-containing compound represented by the formula (D2) is further added to the resin composition. By doing so, the resolution can be improved while improving the adhesion and heat resistance of the relief pattern to be obtained.

(E) Sulfur-containing compound (E) The component is represented by the following general formula (E1):
{Wherein R ₃₄ is a C _{1 to} C ₂₀ organic group or silicon-containing organic group, 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. is there. }
It is a sulfur containing compound represented by these.

For R ₃₄ , examples of the C _{1 to} C ₂₀ organic group include a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a tolyl group, a benzyl group, and the like. Examples include methoxysilylpropyl group, triethoxysilylpropyl group, methyldimethoxysilylpropyl group, methyldiethoxysilylpropyl group, triethoxysilylethyl group and the like.

As R ₃₅ , for example,
Methylamino group, ethylamino group, n-propylamino group, n-butylamino group, n-hexylamino group, n-octylamino group, isopropylamino group, isobutylamino group, t-butylamino group, isoamylamino group, Mono- and dialamino groups such as cyclopentyl group, cyclohexylamino group, dimethylamino group, diethylamino group, dibutylamino group, dicyclohexylamino group;
Aromatic ring-containing amino groups such as phenylamino group, benzylamino group, diphenylamino group;
Heterocyclic-containing amino groups such as picolyl group, aminotriazyl group, furfurylamino group, morpholino group;
Alkoxy groups such as methoxy group, ethoxy group, n-butoxy group, t-butoxy group, hexyloxy group, cyclohexyloxy group;
Alkylaryloxy groups or arylalkyloxy groups such as phenoxy group, benzyloxy group, tolyloxy group;
A heterocyclic ring-containing alkoxy group such as a furfurylalkoxy group and a 2-pyridinylethoxy group;
Alkylthio groups such as methylthio group, ethylthio group, n-butylthio group, t-butylthio group, hexylthio group, cyclohexylthio group or phenylthio group;
Etc.

  (E) It is preferable that the compounding quantity of a sulfur containing compound is 0.1-20 mass parts with respect to 100 mass parts of (A) resin, (AX) photosensitive polyimide precursor, or (AY) polyimide precursor. From the viewpoint of improving heat resistance and adhesion, the content is more preferably 0.5 to 10 parts by mass. (E) By mixing the sulfur-containing compound with 0.1 part by mass or more with respect to 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor, excellent adhesion can be obtained. By being blended and blended at 20 parts by mass or less, excellent heat resistance is maintained.

Other components The fat composition of the present invention may further contain components other than the components (A) to (E).
As other components, a solvent can be used. In that case, the varnish-like negative photosensitive resin composition can be obtained by dissolving the components (A) to (E) in a solvent.
As the solvent, a polar organic solvent is preferably used from the viewpoint of solubility in the (A) resin, the (AX) photosensitive polyimide precursor, or the (AY) polyimide precursor. Specifically, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α -Acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone and the like are used. These can be used alone or in combination of two or more.

  The solvent is, for example, 30 to 1500 masses per 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor, depending on the desired coating thickness and viscosity of the resin composition. Part, preferably 100 to 1000 parts by weight.

  Furthermore, the solvent containing alcohol is preferable from a viewpoint of improving the storage stability of a resin composition. Examples of alcohols include alcohols having an alcoholic hydroxyl group in the molecule and no olefinic double bonds, and specific examples thereof include methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol. Alkyl alcohols such as n-butyl alcohol, isobutyl alcohol and tert-butyl alcohol; lactic acid esters such as ethyl lactate; propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether Propylene glycol monoalkyl ethers such as propylene glycol-2-ethyl ether, propylene glycol-1- (n-propyl) ether, propylene glycol-2- (n-propyl) ether; Glycol methyl ether, ethylene glycol ethyl ether, mono-alcohols such as ethylene glycol -n- propyl ether; 2-hydroxyisobutyric acid esters, ethylene glycol, and dialcohols such as propylene glycol. Among these, alkyl alcohols, lactic acid esters, propylene glycol monoalkyl ethers, and 2-hydroxyisobutyric acid esters are preferable. As the alkyl alcohol, ethyl alcohol is preferable. More preferred are ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, and propylene glycol-1- (n-propyl) ether.

  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% by mass, More preferably, it is 10-30 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, and when it is 50% by mass or less, (A) resin, (AX) The solubility of the photosensitive polyimide precursor or (AY) polyimide precursor is good.

  The resin composition of the present invention may further contain a resin component other than the above-described (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. It is preferable that the compounding quantity of these resin components exists in the range of 0.01-20 mass parts with respect to 100 mass parts of (A) resin, (AX) photosensitive polyimide precursor, or (AY) polyimide precursor. .

When the resin composition of the present invention is photosensitive, the resin composition may contain a photosensitive agent other than the components (B1) and (B2) described above, and a photosensitive agent other than the components (B1) and (B2). As such, a photopolymerization initiator usually used for UV curing 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, fluorenone;
Acetophenone derivatives such as 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone;
Thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone;
Benzyl derivatives such as benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal;
Benzoin derivatives such as benzoin and benzoin methyl ether;
1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propane Dione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (o-benzoyl) oxime, Irgacure OXE01 (trade name, manufactured by BASF), Irgacure OXE02 (trade name, manufactured by BASF Corp.), Adekaoptomer N-1919 (ADEKA) Product name), TR-PBG304 (Changzhou Powerful Electronic New Materials Co., Ltd., product name), R-PBG305 (Changzhou powerful electronic New Materials Co., Ltd., trade name) oximes and the like;
N-aryl glycines such as N-phenyl glycine;
Peroxides such as benzoyl perchloride;
Aromatic biimidazoles;
Etc. are preferred.
One or a mixture of two or more of these may be used. Among the above photosensitive agents, oximes are more preferable from the viewpoint of photosensitivity.

  The blending amount of the photosensitive agent is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor, and photosensitivity. It is preferable that it is 2-15 mass parts from a viewpoint. A photosensitive resin composition having excellent photosensitivity by blending the photosensitive agent with 0.1 part by mass or more with respect to 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor. The photosensitive resin composition which is excellent in thick film sclerosis | hardenability can be obtained by mix | blending in 20 mass parts or less.

Moreover, when the resin composition of this invention is photosensitive, in order to improve photosensitivity, a sensitizer can be arbitrarily mix | blended with a resin composition.
Examples of the sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, and 2,6-bis (4′-diethylaminobenzal). Cyclohexanone, 2,6-bis (4′-diethylaminobenzal) -4-methylcyclohexanone, 4,4′-bis (dimethylamino) chalcone, 4,4′-bis (diethylamino) chalcone, p-dimethylaminocinnamyl Denindanone, p-dimethylaminobenzylideneindanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) iso Naphthothiazole, 1,3-bis (4′-dimethyla Minobenzal) acetone, 1,3-bis (4′-diethylaminobenzal) acetone, 3,3′-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7 -Dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N- Phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phen 5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylaminostyryl) naphtho (1, 2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene and the like. These can be used alone or in combination of, for example, 2 to 5 kinds.

  When the negative photosensitive resin composition contains a sensitizer for improving photosensitivity, the amount of the sensitizer is (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor. It is preferable that it is 0.1-25 mass parts with respect to 100 mass parts of bodies.

  In order to improve the resolution of the relief pattern, a monomer having a photopolymerizable unsaturated bond different from the component (C) can be blended in the resin composition. As such a monomer, a (meth) acryl compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferable, and is not limited, but ethylene glycol represented by diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, etc. Polyethylene glycol mono- or diacrylate and methacrylate; propylene glycol or polypropylene glycol mono- or diacrylate and methacrylate; glycerol mono-, di- or triacrylate and methacrylate; cyclohexane diacrylate and dimethacrylate; 1,4-butanediol diacrylate And dimethacrylate; 1,6-hexanediol diacrylate and dimethacrylate; neopentyl glycol diacrylate Over preparative and dimethacrylate; mono- or di-acrylates and methacrylates of bisphenol A; benzene trimethacrylate; isobornyl acrylate and methacrylate; acrylamides and derivatives thereof; methacrylamide and derivatives thereof.

  In order to improve the resolution of the relief pattern, when the negative photosensitive resin composition contains the monomer having the above-described photopolymerizable unsaturated bond, the amount of the monomer is (A) resin, (AX ) It is preferable that it is 1-50 mass parts with respect to 100 mass parts of photosensitive polyimide precursor or (AY) polyimide precursor.

  In order to improve the adhesiveness between the film formed using the resin composition of the present invention and the substrate, an adhesion assistant can be blended in the resin composition. Adhesion aids include γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3- Methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) succinimide N- [3- (triethoxysilyl) propyl] phthalamic acid, benzophenone-3,3′-bis (N- [3-triethoxysilyl] propylamide) -4,4′-dicarboxylic acid, benzene-1, 4-bis (N- [3-trie Silane coupling agents such as (toxisilyl) propylamide) -2,5-dicarboxylic acid, 3- (triethoxysilyl) propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane; and aluminum tris (ethyl acetoacetate), Examples thereof include aluminum-based adhesion assistants such as aluminum tris (acetylacetonate) and ethyl acetoacetate aluminum diisopropylate.

  Among these adhesion assistants, a silane coupling agent is preferable from the viewpoint of adhesive strength. When the negative photosensitive resin composition contains an adhesion assistant, the compounding amount of the adhesion assistant is based on 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor, or (AY) polyimide precursor. , Preferably in the range of 0.5 to 25 parts by mass.

  In order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition when stored in a solution containing a solvent, a thermal polymerization inhibitor can be blended in the photosensitive resin composition. Examples of thermal polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6 -Di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N- Sulfopropylamino) phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt and the like are used.

  The blending amount of the thermal polymerization inhibitor in the photosensitive resin composition is 0.005 to 12 parts by mass with respect to 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor. It is preferable that it is the range of these.

  If desired, a crosslinking agent may be added to the resin composition. The crosslinking agent may crosslink the (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor when the relief pattern formed using the resin composition of the present invention is heat-cured. Or the crosslinking agent itself can form a crosslinked network. The crosslinking agent can further enhance the heat resistance and chemical resistance of the cured film formed from the negative photosensitive resin composition. As the crosslinking agent, amino resins and derivatives thereof are preferably used, and among them, urea resins, glycol urea resins, hydroxyethylene urea resins, melamine resins, benzoguanamine resins, 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), UFR-65 (manufactured by Nippon Cytec), and MW-390 ( Manufactured by Nippon Carbide Corporation).

  In order to maintain a balance between heat resistance and chemical resistance and performances other than these, the blending amount of the crosslinking agent in the resin composition is (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide. It is preferable that it is 0.5-20 mass parts with respect to 100 mass parts of precursors, More preferably, it is 2-10 mass parts. When the 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, the storage stability is excellent.

  When using the board | substrate which consists of copper or a copper alloy, in order to suppress discoloration of a board | substrate surface, an azole compound can be mix | blended with a resin composition. Examples of the azole compound include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, and 4-t-butyl-5. -Phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1- (2-dimethylaminoethyl) triazole, 5-benzyl-1H-triazole, hydroxyphenyl Triazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5- Bis (α, α-dimethylben Dil) phenyl] -benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -benzotriazole 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5 -Methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl -1H-tetrazole, 5-amino-1H-tetra Lumpur, 1-methyl -1H- tetrazole, and the like. Preferred azole compounds include tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. These azole compounds may be used alone or in a mixture of two or more.

  The compounding quantity of the azole compound in a resin composition may be 0.1-20 mass parts with respect to 100 mass parts of (A) resin, (AX) photosensitive polyimide precursor, or (AY) polyimide precursor. Preferably, it is 0.5-5 mass parts from a viewpoint of photosensitivity. When the blending amount of the azole compound with respect to 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor is 0.1 parts by mass or more, the resin composition of the present invention is made of copper or When formed on a copper alloy, discoloration of the copper or copper alloy surface is suppressed, and when it is 10 parts by mass or less, the photosensitivity is excellent.

  Moreover, in order to suppress discoloration of the surface of the board | substrate which consists of copper or a copper alloy, a hindered phenol compound can be mix | blended with a resin composition. Examples of hindered phenol compounds include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, and octadecyl-3- (3,5-di-t-butyl-4. -Hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4'-methylenebis (2,6-di-t-butylphenol), 4, 4′-thio-bis (3-methyl-6-tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-t -Butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphene) ) Propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N ′ hexamethylenebis (3,5-di-t) -Butyl-4-hydroxy-hydrocinnamamide), 2,2'-methylene-bis (4-methyl-6-t-butylphenol), 2,2'-methylene-bis (4-ethyl-6-t-) Butylphenol), pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanate Nurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3-hydroxy 2,6-Dimethyl-4-isopropylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-t-butyl- 3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-s-butyl- 3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris [4- (1-ethyl Propyl) -3-hydroxy-2,6-dimethylbenzyl] -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris [4-triethyl Methyl-3-hydroxy-2,6-dimethylbenzyl] -1,3,5 Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (3-hydroxy-2,6-dimethyl-4-phenylbenzyl) -1,3,5-triazine -2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl) -1,3,5 Triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl) -1 , 3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -tri 1,3,5-tris (4-t-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H , 5H) -trione, 1,3,5-tris (4-t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-3-hydroxy-2-methylbenzyl) -1,3,5-triazine-2,4,6- (1H , 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H , 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-5-ethyl-3) Hydroxy-2-methylbenzyl) -1,3,5-triazine -2,4,6- (1H, 3H, 5H) - but trione, etc., but is not limited thereto. Among these, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H ) -Trione and the like are preferred.

  It is preferable that the compounding quantity of a hindered phenol compound is 0.1-20 mass parts with respect to 100 mass parts of (A) resin, (AX) photosensitive polyimide precursor, or (AY) polyimide precursor, and light. From the viewpoint of sensitivity, it is more preferably 0.5 to 10 parts by mass. When the blending amount of the hindered phenol compound with respect to 100 parts by mass of (A) resin, (AX) photosensitive polyimide precursor or (AY) polyimide precursor is 0.1 parts by mass or more, for example, on copper or copper alloy When the resin composition of the present invention is formed, discoloration / corrosion of copper or a copper alloy is prevented, and when it is 20 parts by mass or less, the photosensitivity is excellent.

<Method for Manufacturing Cured Relief Pattern and Semiconductor Device>
When the resin composition of the present invention is photosensitive, the following steps:
(1) Applying the photosensitive resin composition described above on a substrate, and forming a photosensitive resin layer on the substrate;
(2) exposing the photosensitive resin layer;
(3) developing the photosensitive resin layer after the exposure to form a relief pattern;
(4) subjecting the relief pattern to a heat treatment to form a cured relief pattern;
The manufacturing method of the hardening relief pattern containing can be provided. Hereinafter, typical aspects of each process will be described.

(1) The process of apply | coating the photosensitive resin composition on a board | substrate, and forming a photosensitive resin layer on this board | substrate At this process, the photosensitive resin composition of this invention is apply | coated on a base material, and as needed Then, it is dried to form a photosensitive resin layer. As a coating method, a method conventionally used for coating a photosensitive resin composition, for example, a method of coating with a spin coater, bar coater, blade coater, curtain coater, screen printing machine, etc., spray coating with a spray coater A method or the like can be used.

  If necessary, the coating film made of the photosensitive resin composition can be dried. As a drying method, methods such as air drying, heat drying with an oven or a hot plate, and vacuum drying are used. In addition, drying of the coating film causes modification of (A) resin in the photosensitive resin composition, or imidization of (AX) photosensitive polyimide precursor, (AY) polyimide precursor (polyamic acid ester). It is desirable to perform under such conditions. Specifically, when performing air drying or heat drying, drying can be performed at 20 ° C. to 140 ° C. for 1 minute to 1 hour. Thus, a photosensitive resin layer can be formed on the substrate.

(2) Step of exposing photosensitive resin layer In this step, the photosensitive resin layer formed as described above is exposed through a photomask or reticle having a pattern using an exposure apparatus such as a contact aligner, mirror projection, or stepper. Alternatively, direct exposure is performed with an ultraviolet light source or the like.

  Thereafter, post-exposure baking (PEB) and / or pre-development baking with any combination of temperature and time may be performed as necessary for the purpose of improving photosensitivity. The range of the baking conditions is preferably 40 to 120 ° C. and the time of 10 to 240 seconds, but is not limited to this range as long as the various characteristics of the photosensitive resin composition of the present invention are not impaired.

(3) Step of developing the exposed photosensitive resin layer to form a relief pattern In this step, the unexposed portion of the exposed photosensitive resin layer is developed and removed. As a developing method for developing the photosensitive resin layer after the exposure (irradiation), a conventionally known photoresist developing method, for example, a rotary spray method, a paddle method, an immersion method with ultrasonic treatment, or the like can be used. A method can be selected and used. Further, after development, for the purpose of adjusting the shape of the relief pattern, post-development baking at any combination of temperature and time may be performed as necessary.

  The developer used for development is preferably a good solvent for the photosensitive resin composition or a combination of the good solvent and the poor solvent. As the good solvent, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferable and poor. As the solvent, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water and the like are preferable. When mixing and using a good solvent and a poor solvent, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the photosensitive resin composition. Also, two or more of each solvent, for example, several types may be used in combination.

(4) Step of forming a relief pattern by subjecting the relief pattern to heat treatment In this step, the relief pattern obtained by the above development is heated to dilute the photosensitive component, and (A) resin, (AX) The photosensitive polyimide precursor or (AY) polyimide precursor is converted into a cured relief pattern by heat curing. As a method of heat curing, various methods such as a method using a hot plate, a method using an oven, and a method using a temperature rising oven capable of setting a temperature program can be selected. Heating can be performed, 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 provided with the hardening relief pattern obtained by the manufacturing method of the hardening relief pattern demonstrated above can also be provided. More specifically, it is possible to provide a semiconductor device having a base material that is a semiconductor element and a cured relief pattern of polyimide formed on the base material by the above-described cured relief pattern manufacturing method. The present invention can also be applied to a method for manufacturing a semiconductor device using a semiconductor element as a base material and including the above-described method for manufacturing a cured relief pattern as part of the process. The semiconductor device of the present invention has a cured relief pattern having a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a bump structure by the method for producing a cured relief pattern described above. It can be formed as a protective film of a semiconductor device and can be manufactured by combining a method for manufacturing a cured relief pattern and a known method for manufacturing a semiconductor device.

<Resin film>
As the component (A), polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyhydroxyamide that can be a polyoxazole precursor, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, It contains at least one resin selected from the group consisting of polybenzimidazole, polybenzothiazole, and phenol resin, and has a crosslinking density of 1.0 × 10 ⁻⁴ mol / cm ³ or more, 3.0 × 10 ⁻³ mol / A resin film having a cm ³ or less and a 5% weight loss temperature of 250 ° C. or more and 400 ° C. or less is also an embodiment 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 to the polybenzoxazole resin, the component (A) includes polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, and At least one resin selected from the group consisting of polybenzothiazole is preferred. In the resin film, the component (A) is preferably contained in an amount of 50% by mass or more, more preferably 70% by mass or more, based on the total mass of all the 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 in terms of polystyrene by gel permeation chromatography from the viewpoint of heat resistance and mechanical properties after heat treatment, and is 5,000 or more. It is more preferable that The upper limit of the weight average molecular weight is preferably 100,000 or less.

The crosslink density is the number of moles of chemically cross-linked functional groups contained in 1 cm ³ of the resin film. Crosslinking is a method in which a monomer having a crosslinkable functional group is copolymerized in component (A), and these crosslinkable functional groups are reacted with each other; (A) component is chemically crosslinked with component (A). A method of crosslinking the molecular chains of the component (A) via the crosslinking agent; adding a polyfunctional monomer to the component (A) to crosslink the polyfunctional monomers This is achieved by the method. When crosslinking occurs in the resin, the storage elastic modulus above the glass transition temperature increases according to the crosslinking density. At this time, when the elasticity is caused only by ideal rubber elasticity, the following relational expression between the crosslinking density and the storage elastic modulus:
n = E '/ 3RT
{N: Crosslink density, E ′: Storage modulus, R: Gas constant, T: Absolute temperature}
Is known to hold.

  Therefore, in the case of an ideal rubber elastic body, the crosslink density can be obtained by measuring the storage elastic modulus above the glass transition temperature of the resin film. The storage elastic modulus 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, this relational expression does not necessarily hold strictly between the crosslinking density and the storage elastic modulus. In that case, the number of crosslinkable functional groups contained in the resin film and the reaction rate thereof were confirmed while using a dynamic viscoelasticity measuring device, for example, to confirm that the storage elastic modulus above the glass transition temperature was increased. Can be determined by a spectroscopic method, the crosslinking density can be calculated therefrom.

The crosslinking density of the resin film used in the present invention is 1.0 × 10 ⁻⁴ mol / cm ³ or more, 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 ³ or less. When the crosslinking density is less than 1.0 × 10 ⁻⁴ mol / cm ³ , the adhesion between the resin film and the polybenzoxazole resin is not sufficient. When the crosslink density exceeds 3.0 × 10 ⁻³ mol / cm ³ , the resin film becomes brittle and is not suitable for uses such as a passivation film, a buffer coat film, and an interlayer insulating film assumed in the present invention.

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

  The resin film can be obtained by, for example, applying a solution in which a component that is a precursor of the resin film is dissolved on a base material and heating at a temperature of 250 ° C. or lower. There may be an exposure step before heating. At this time, by setting the heating temperature to 250 ° C. or lower, the resin film is formed on a base material including a resin substrate having a glass transition temperature of 250 ° C. or lower, or the heating temperature is set to 200 ° C. or lower. Thereby, the said resin film can be formed on the base material containing the resin substrate whose glass transition temperature is 200 degrees C or less, and a laminated body can be obtained.

  The resin composition of the present invention is useful for applications such as interlayer insulation of multilayer circuits, cover coats of flexible copper-clad plates, solder resist films, and liquid crystal alignment films, in addition to application to semiconductor devices as described above. is there.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In Examples, Comparative Examples, and Production Examples, physical properties of resins, resin films, and resin compositions were measured and evaluated according to the following methods.

(1) Weight average molecular weight The weight average molecular weight (Mw) of resin was measured by the gel permeation chromatography method (standard polystyrene conversion). The column used for the measurement was Shodex (trade name) 805M / 806M series manufactured by Showa Denko KK, and Shodex STANDARD SM-105 manufactured by Showa Denko KK was selected as the standard monodisperse polystyrene, and the developing solvent was N-methyl. 2-pyrrolidone, and Shodex (trade name) RI-930 manufactured by Showa Denko was used as a detector.

(2) Adhesion evaluation with polybenzoxazole resin A resin film precursor or a photosensitive resin composition is spin-coated on a 6-inch silicon wafer coated and cured with polybenzoxazole resin, and dried to a thickness of about 10 μm. Was formed as a resin film precursor or a photosensitive resin layer. This coating film was exposed by irradiating 1500 mJ / cm ² energy with an i-line stepper NSR2005i8A (manufactured by Nikon Corporation) using a reticle with a test pattern. Next, the coating film formed on the wafer is spray-developed with a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd.) using cyclopentanone, rinsed with propylene glycol methyl ether acetate, and uncoated. The exposed portion was developed and removed to obtain a relief pattern of the resin film precursor or the photosensitive resin composition.

A wafer having a relief pattern formed thereon is heat-treated at 200 to 300 ° C. for 2 hours in a nitrogen atmosphere using a temperature rising programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd., Japan) A cured relief pattern of a resin film or a photosensitive resin composition was obtained on the substrate on which the oxazole resin was applied and cured. The film thickness was measured using a Tencor P-15 type step gauge (manufactured by KLA Tencor). For each pattern obtained, 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 opening of the obtained 20 μm pattern is ½ or more of the corresponding pattern mask opening area, and there is no peeling.
Defect: 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 8.5 μm thick coating film. This coating film was irradiated with energy of 500 mJ / cm ² by Prisma GHI (manufactured by Ultratech, USA) through a mask with a test pattern. Next, the irradiated coating film is spray-developed with a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd.) using cyclopentanone, rinsed with propylene glycol methyl ether acetate, and unexposed areas. Was removed by development to obtain a relief pattern.

A silicon wafer having this relief pattern was immersed in liquid nitrogen, and a 50 μm wide line and space (1: 1) portion was cleaved in a direction perpendicular to the line. The obtained cross section was observed by SEM (Hitachi High-Technologies S-4800 type). 1A to 1E, the taper angle was evaluated by a method including the following steps 1 to 5:
1. Drawing the upper and lower sides of the opening (FIG. 1A);
2. Determining the height of the opening (FIG. 1B);
3. Draw a straight line (center line) parallel to the upper and lower sides through the central part of the height (FIG. 1C);
4). 4. Find the intersection (center point) between the center line and the opening pattern (FIG. 1D); A tangent line is drawn in accordance with the inclination of the pattern at the center point, and an angle formed by the tangent line and the lower side is regarded as a taper angle (FIG. 1E).

The above wafer was heated on a silicon wafer at 200 to 390 ° C. for 2 hours in a nitrogen atmosphere using a temperature rising programmed curing furnace (VF-2000, manufactured by Koyo Lindberg, Japan). A cured relief pattern having a thickness of about 4 to 5 μm was obtained.
About this relief pattern, the film thickness was measured using a Tencor P-15 type step gauge (manufactured by KLA Tencor), and the taper angle of the line and space (1: 1) portion was determined in the same manner as described above.

(4) Evaluation of minimum opening pattern size The resin composition was spin-coated on a 6-inch silicon wafer and dried to form an 8.5 μm thick coating film. This coating film was irradiated with energy of 500 mJ / cm ² by Prisma GHI (manufactured by Ultratech, USA) using a mask with a test pattern. Next, the irradiated coating film is spray-developed with a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd.) using cyclopentanone, rinsed with propylene glycol methyl ether acetate, and unexposed areas. Was removed by development to obtain a relief pattern.

The wafer on which this relief pattern was formed was heat-treated at 200 to 390 ° C. for 2 hours in a nitrogen atmosphere using a temperature rising program type curing furnace (VF-2000 type, manufactured by Koyo Lindberg, Japan), A cured relief pattern of polyimide having a thickness of about 4 to 5 μm was obtained on a silicon wafer and a copper substrate, respectively.
The film thickness was measured using a Tencor P-15 type step gauge (manufactured by KLA Tencor). About the pattern obtained on Si, the pattern shape and the width | variety of a pattern part were observed under the optical microscope, and the size of the minimum opening pattern was calculated | required.

(5) Measurement of glass transition temperature (Tg) of cured film On 6-inch silicon wafer (Fujimi Electronics Co., Ltd., Japan, thickness 625 ± 25 μm) serving as a substrate, and 200 nm thick Ti and The resin composition was spin-coated on the sputtered bodies obtained by sputtering 400 nm thick Cu in this order so that the cured film thickness was about 4 to 5 μm. Next, when the resin composition was photosensitive, energy of 500 mJ / cm ² was irradiated by a parallel light mask aligner PLA-501FA (manufactured by Canon Inc., Japan). This irradiation was not performed when the resin composition was not photosensitive.

Then, the cured film was obtained by heating at 200-390 degreeC for 2 hours and thermosetting in nitrogen atmosphere. The obtained cured film was peeled from the wafer to obtain a cured tape.
The obtained cured tape was measured with a thermomechanical test apparatus (TMA-50 manufactured by Shimadzu Corporation) at a load of 200 g / mm ² , a heating rate of 10 ° C./min, and a temperature range of 20 to 500 ° C. The tangential intersection of the thermal yield point of the cured tape in the measurement chart with the amount taken on the vertical axis was defined as the glass transition temperature (Tg).

(6) Measurement of Si Adhesion and Cu Adhesion of Cured Film On a 6-inch silicon wafer (made by Fujimi Electronics Co., Ltd., Japan, thickness 625 ± 25 μm) as a substrate, and 200 nm thick Ti on this silicon wafer The resin composition was spin-coated on the sputters obtained by sputtering Cu having a thickness of 400 nm in this order so that the film thickness after curing was about 4 to 5 μm. Next, when the resin composition was photosensitive, energy of 500 mJ / cm ² was irradiated by a parallel light mask aligner PLA-501FA (manufactured by Canon Inc., Japan). This irradiation was not performed when the resin composition was not photosensitive.

Then, the cured film was obtained by heating for 2 hours at 200 ° C. to 390 ° C. in a nitrogen atmosphere.
The adhesion of the obtained cured film to Si or Cu was evaluated by a cross-cut test (JIS K5400). That is, scratches with a cutter knife so that 100 squares of 1 mm square can be formed on the coating film, a cellophane (registered trademark) tape is applied from above, and the cellophane is adhered until it is free from bubbles, and then peeled off. Evaluation was performed by counting the number of squares that remained on the substrate without adhering to the (registered trademark) tape.

(7) Crosslink density After peeling the resin film from the substrate, the temperature was increased from 30 ° C. to 400 ° C. at 5 ° C./min using a dynamic viscoelasticity measuring device Leo Vibron model DDV-01FP (manufactured by Orientec Co., Ltd.). However, the storage elastic modulus at each temperature was obtained by applying minute vibrations at frequencies of 3.5, 11, 35, and 110 Hz. Moreover, the reaction rate of the crosslinkable group in a resin film was calculated | required using 380 type | mold FTIR (made by a Nicolet company), and the crosslinking density was calculated from it.

(8) 5% weight loss temperature After peeling the resin film from the substrate, the temperature was increased from 30 ° C. to 500 ° C. at 10 ° C./min under nitrogen using a thermogravimetric measuring device (TGA-50 manufactured by Shimadzu Corporation). The temperature at which the weight was reduced by 5% from the initial value was determined.

<Production Example 1> (Synthesis of polyimide precursor A (polymer A) as component (A))
Place 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in a 2 liter separable flask, add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone and stir at room temperature. While stirring, 81.5 g of pyridine was added to obtain a reaction mixture. After completion of the exothermic reaction, the mixture was allowed to cool to room temperature and left for 16 hours.

  Next, under ice cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4′-diaminodiphenyl ether (DADPE). A suspension of 93.0 g in γ-butyrolactone 350 ml was added over 60 minutes with stirring. After further stirring for 2 hours at room temperature, 30 ml of ethyl alcohol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate generated 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 form a precipitate consisting of a crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 liter of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate a polymer, and the resulting precipitate was filtered off, and then vacuum dried to obtain a powdered polymer (polyimide precursor A (hereinafter referred to as “polymer A”). Also called))). When the molecular weight of the polyimide precursor A was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000.

<Production Example 2> (Synthesis of polyimide precursor B (polymer B) as component (A))
The above production example except that 147.1 g of 3,3′4,4′-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4′-oxydiphthalic dianhydride of Production Example 1. Reaction was carried out in the same manner as described in 1, to obtain a polyimide precursor B (hereinafter also referred to as “polymer B”). When the molecular weight of the polyimide precursor B was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.

<Production 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 dissolved by stirring at room temperature. Thereafter, 155.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) was added and reacted at 80 ° C. for 5 hours to obtain a solution of polymer C (polyamide acid which is a polyimide precursor). When the molecular weight of the polymer A-1 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000.

<Production 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. Then, 26.4 g of 3-ureidopropyltriethoxysilane was dropped from the dropping funnel, and the mixture was allowed to stand at room temperature for 5 hours. By stirring for a period of time, a solution of silicon-containing compound D-1 was obtained.

<Example 1>
The photosensitive resin composition was prepared with the following method using the polyimide precursor A (polymer A) and the polyimide precursor B (polymer B), and the prepared composition was evaluated. As component (A), polymer A50g and polymer B50g, as component (B), Adekaoptomer NCI831 (manufactured by ADEKA, trade name, 0.001 wt% solution g-line, h-line, and i-line absorbance are respectively (0), 0.13, and 0.22), 2 g as component (C), 10 g of 4,4′-bismaleimide diphenylmethane, 4 g of hexamethoxymethylmelamine, and 8 g of tetraethylene glycol dimethacrylate, (D) As a component, 3 g of silicon-containing compound D-1 and 0.05 g of 2-nitroso-1-naphthol were dissolved in a mixed solvent composed of 80 g of N-methylpyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate. The viscosity of the resulting solution was adjusted to about 35 poise by further adding a small amount of the mixed solvent to obtain a photosensitive resin composition.
Polybenzoxazole (PBO) resin when the composition is applied to a silicon wafer according to the method for evaluating adhesion to (2) polybenzoxazole resin, dried, exposed, developed, and thermally cured at 200 ° C. The adhesion on the substrate was “good”.

<Example 2>
In Example 1, a negative photosensitive resin composition was prepared by changing the amount of 4,4′-bismaleimide diphenylmethane as component (C) in the present invention to 20 g, and the same evaluation as in Example 1 was performed. went. It was "good" as a result of evaluating the adhesiveness on a PBO resin base material. However, the thermosetting temperature of this composition was 200 degreeC at this time.

<Example 3>
A photosensitive resin composition was prepared by changing the component (C) of Example 1 to bis (3-ethyl-5-methyl-4-maleimidophenyl) methane in the present invention, and the same evaluation as in Example 1 was performed. went. It was "good" as a result of evaluating the adhesiveness on a PBO resin base material. However, the thermosetting temperature of this composition was 200 degreeC at this time.

<Example 4>
In Example 3, a photosensitive resin composition was prepared by changing the blending amount of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane as component (C) in the present invention to 20 g. Evaluation similar to 3 was performed. It was "good" as a result of evaluating the adhesiveness on a PBO resin base material. However, the thermosetting temperature of this composition was 200 degreeC at this time.

<Example 5>
A photosensitive resin composition was prepared by changing the component (C) in Example 1 of the present invention to N-phenylmaleimide, and the same evaluation as in Example 1 was performed. It was "good" as a result of evaluating the adhesiveness on a PBO resin base material. However, the thermosetting temperature of this composition was 200 degreeC at this time.

<Example 6>
In Example 1, the photosensitive resin composition was prepared by changing the component (C) in the present invention to N, N ′, N ″-[nitrilotris (ethylene)] tris (maleimide). The same evaluation was performed. It was "good" as a result of evaluating the adhesiveness on a PBO resin base material. However, the thermosetting temperature of this composition was 200 degreeC at this time.

<Example 7>
In Example 2, the component (C) in the present invention is changed to isocyanuric acid triacrylate, which is a polyfunctional methacrylate whose homopolymer has a glass transition temperature of 200 ° C. or higher, to prepare a photosensitive resin composition, The same evaluation as in Example 2 was performed. It was "good" as a result of evaluating the adhesiveness on a PBO resin base material. However, the thermosetting temperature of this composition was 200 degreeC at this time.

<Comparative Example 1>
The negative photosensitive resin composition was prepared by removing 4,4′-bismaleimide diphenylmethane as the component (C) in the present invention of Example 1, and the same evaluation as in Example 1 was performed. As a result of evaluating the adhesion on the PBO resin base material, it was “defective”. However, the thermosetting temperature of this composition was 200 degreeC at this time.

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

Explanation of abbreviations in Table 1 B1: Adekaoptomer 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 ″-[nitrilotris (ethylene ]] Tris (maleimide)
C5: Isocyanuric acid triacrylate D1: Silicon-containing compound D-1

<Example 8>
As the (AX) component, polymer A 50 g and polymer B 50 g, as the (B) component Irgacure OXE03 (trade name, g-line, h-line, and i-line absorbance of 0.001 wt% solution are 0, 0, 2 g), tetraethylene glycol dimethacrylate 8 g and 2-nitroso-1-naphthol 0.05 g, and diphenylacetamide 5 g, N- (3- (triethoxysilyl) propyl) phthalamic acid 0. 5 g and 0.5 g of benzophenone-3,3′-bis (N- (3-triethoxysilyl) propylamide) -4,4′-dicarboxylic acid in a mixed solvent consisting of N-methylpyrrolidone and ethyl lactate (weight) Photosensitive resin group by adjusting the amount of the solvent so that the viscosity is about 35 poises. Things to obtain a solution.
About this composition, it evaluated by the taper angle evaluation of the above-mentioned (3) opening pattern, and (4) minimum opening pattern size evaluation method.

<Example 9>
Polymer (A) 50 g and Polymer B 50 g as component (AX), Irgacure OXE03 2 g as component (B), 16 g of 4,4′-bismaleimide diphenylmethane, 8 g of tetraethylene glycol dimethacrylate and 2-nitroso-1-naphtho as component (C) 0.05 g of diphenylacetamide, 5 g of diphenylacetamide, 0.5 g of N- (3- (triethoxysilyl) propyl) phthalamic acid, and benzophenone-3,3′-bis (N- (3-triethoxysilyl) propylamide ) -4,4'-dicarboxylic acid 0.5g is dissolved in a mixed solvent (mass ratio 8: 2) consisting of N-methylpyrrolidone and ethyl lactate, and the amount of the solvent is adjusted so that the viscosity is about 35 poise. As a result, a photosensitive resin composition solution was obtained.
This composition was evaluated in the same manner as in Example 8.

<Example 10>
In Example 9, instead of 2 g of Irgacure OXE03 as component (B), Adekaoptomer NCI831 (manufactured by ADEKA, trade name, g-line, h-line, and i-line absorbance of 0.001 wt% solution is 0, A photosensitive resin composition solution was prepared in the same manner as in Example 9 except that 2 g (0.13 and 0.22) were used.
This composition was evaluated in the same manner as in Example 8.

<Example 11>
In Example 9, as component (B), TR-PBG340 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd., trade name, g-line, h-line, and i-line absorbance of 0.001 wt% solution was 0.04, 0, respectively. A photosensitive resin composition solution was prepared in the same manner as in Example 9 except that 2 g (0.06 and 0.04) were used.
This composition was evaluated in the same manner as in Example 8.

<Comparative example 2>
In Example 8, as an alternative component of the component (B), TR-PBG304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd., trade name, g-line, h-line, and i-line absorbance of 0.001 wt% solution was 0, respectively. A photosensitive resin composition was prepared in the same manner as in Example 8, except that 4 g) were used.
This composition was evaluated in the same manner as in Example 8.

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

Explanation of Abbreviations in Table 2 (B) Component
B1: Irgacure OXE03 (trade name, manufactured by BASF)
B2: Adekaoptomer NCI831 (made by ADEKA, trade name)
B3: TR-PBG340 (Changzhou Power Electronics New Materials Co., Ltd., trade name)
-(C) component-
C1: 4,4'-Bismaleimide diphenylmethane-Alternative component-
B4: TR-PBG304 (Changzhou Power Electronics New Materials Co., Ltd., trade name)

<Example 12>
(AY) Polymer C 100 g as component, Irgacure OXE03 (trade name) manufactured by BASF as component (B) and 3 g of silicon-containing compound D-1 as component (D), a mixed solvent comprising N-methylpyrrolidone and ethyl lactate ( A resin composition was obtained by adjusting the amount of the solvent so that it was dissolved in a mass ratio of 8: 2) and the viscosity was about 35 poise.
The resin composition was evaluated by (5) measurement of 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.

<Example 13>
(AY) component A 50 g and polymer B 50 g, (B) component Irgacure OXE03 (manufactured by BASF, trade name) 4 g, (D) component silicon-containing compound D-1 3 g, tetraethylene glycol dimethacrylate 8 g, 2- 0.05 g of nitroso-1-naphthol and 5 g of diphenylacetamide are dissolved in a mixed solvent (mass ratio 8: 2) composed of N-methylpyrrolidone and ethyl lactate so that the viscosity is about 35 poise. The resin composition was obtained by adjusting the amount of.
The resin composition was evaluated by (5) measurement of 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.

<Example 14>
(AY) Component A50g and Polymer B50g, (B) Component Irgacure OXE3 (trade name, manufactured by BASF Corp.) 4g, (D) Silicon-containing compound D-1 3g and A-1160 (3-ureido) 3 g of a 50% by mass solution of propyltriethoxysilane (manufactured by Momentive) as a methanol solution, 8 g of tetraethylene glycol dimethacrylate, 0.05 g of 2-nitroso-1-naphthol, and 5 g of diphenylacetamide were added to N-methylpyrrolidone. And the resin composition was obtained by adjusting the quantity of a solvent so that it might melt | dissolve in the mixed solvent (mass ratio 8: 2) which consists of ethyl lactate, and a viscosity might be set to about 35 poise.
The resin composition was evaluated by (5) measurement of 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.

<Example 15>
In Example 14, 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 ° C to 390 ° C.

<Example 16>
(AY) component 50 g of polymer A and polymer B 50 g, (B) component Adeka optomer NCI831 (trade name) 4 g, (C) component 4,4′-bismaleimide diphenylmethane 16 g, (D) component 3 g of silicon-containing compound D-1 and A-1160 (50% by mass solution of 3-ureidopropyltriethoxysilane, manufactured by Momentive) as a methanol solution, 8 g of tetraethylene glycol dimethacrylate, 2-nitroso-1-naphtho 0.05 g of diphenylacetamide and 5 g of diphenylacetamide are dissolved in a mixed solvent composed of N-methylpyrrolidone and ethyl lactate (mass ratio 8: 2), and the amount of the solvent is adjusted so that the viscosity is about 35 poise. A resin composition was obtained.
The resin composition was evaluated by (5) measurement of 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.

<Example 17>
A resin composition was prepared in the same manner as in Example 16 except that the component (C) was changed from 4,4′-bismaleimide diphenylmethane to bis (3-ethyl-5-methyl-4-maleimidophenyl) methane in Example 16. Got.
The resin composition was evaluated by (5) measurement of 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.

<Example 18>
In Example 16, a resin composition was obtained in the same manner as in Example 16 except that 3 g of dicyclohexylthiourea was used as the (E) component instead of the (D) component.
The resin composition was evaluated by (5) measurement of 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.

<Comparative Example 3>
In Example 12, 0.5 g of N- (3- (triethoxysilyl) propyl) phthalamic acid and benzophenone-3,3′-bis (N- (3-triethoxysilyl) propyl were used as alternative components for component (D). A resin composition was obtained in the same manner as in Example 12 except that 0.5 g of amide) -4,4′-dicarboxylic acid was used.
The resin composition was evaluated by (5) measurement of 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.

<Comparative Example 4>
In Example 14, as an alternative component of component (D), 0.5 g of N- (3- (triethoxysilyl) propyl) phthalamic acid and benzophenone-3,3′-bis (N- (3-triethoxysilyl) A resin composition was obtained in the same manner as in Example 14 except that 0.5 g of propylamide) -4,4′-dicarboxylic acid was used.
The resin composition was evaluated by (5) measurement of 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.

<Comparative Example 5>
In Example 15, as an alternative component of component (D), 0.5 g of N- (3- (triethoxysilyl) propyl) phthalamic acid and benzophenone-3,3′-bis (N- (3-triethoxysilyl) A resin composition was obtained in the same manner as in Example 15 except that 0.5 g of propylamide) -4,4′-dicarboxylic acid was used.
The resin composition was evaluated by (5) measurement of 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 abbreviations in Table 3 B1: Irgacure OXE03 (trade name, manufactured by BASF)
B2: Adekaoptomer NCI831 (made by ADEKA, trade name)
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)
D3: N- (3- (triethoxysilyl) propyl) phthalamic acid / benzophenone-3,3′-bis (N- (3-triethoxysilyl) propylamide) -4,4′-dicarboxylic acid

<Example 19>
As component (A), 50 g of polymer A and 50 g of polymer B were added to Adekaoptomer NCI831 (trade name, 0.001 wt% solution g-line, h-line, and i-line absorbance were 0, 0.13, and 0.2 g), 4 g of 4,4′-bismaleimide diphenylmethane, 3 g of silicon-containing compound D-1 and 0.05 g of 2-nitroso-1-naphthol, together with N-methylpyrrolidone (hereinafter referred to as NMP) ) A solution was obtained by dissolving in a mixed solvent consisting of 80 g and 20 g of ethyl lactate. The viscosity of the obtained solution was adjusted to about 35 poise 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 method for evaluating adhesion to the polybenzoxazole resin described in (2) above, dried, exposed, developed, and thermally cured at 200 ° C. to obtain a resin film. At this time, the adhesion on the polybenzoxazole (PBO) resin substrate was “good”.
The above-mentioned (7) crosslinking density was determined to be 7.0 × 10 ⁻⁴ mol / cm ³ from the reaction rate, composition, and density of maleimide by IR. Moreover, the storage elastic modulus in 110 Hz and 300 degreeC was 0.08 GPa, and the above-mentioned (8) 5% weight reduction | decrease temperature was 340 degreeC.

<Example 20>
In Example 19, a photosensitive resin composition was prepared in the same manner as in Example 19 except that the amount of 4,4′-bismaleimide diphenylmethane was changed to 20 g.
The composition was applied to a silicon wafer according to the method for evaluating adhesion to the polybenzoxazole resin described in (2) above, dried, exposed, developed, and thermally cured at 200 ° C. to obtain a resin film. At this time, the adhesion on the polybenzoxazole (PBO) resin substrate was “good”.
Also, the above-mentioned (7) cross-linking density, the reaction rate and composition of the maleimide by IR, was determined to be 1.4 × ¹⁰ -3 mol / cm ³ from the densities. Moreover, the storage elastic modulus in 110 Hz and 300 degreeC was 0.16 GPa, and the above-mentioned (8) 5% weight reduction | decrease temperature was 370 degreeC.

<Comparative Example 6>
A resin composition was prepared in the same manner as in Example 19 except that 4,4′-bismaleimide diphenylmethane was not added in Example 19, and a thermosetting resin film of the composition was obtained. At this time, the adhesion on the polybenzoxazole (PBO) resin base material evaluated according to the method for evaluating the adhesion with the polybenzoxazole resin (2) described above was “poor”.
The above-mentioned (7) crosslinking density was determined to be 0 mol / cm ³ from the reaction rate, composition, and density of maleimide by IR. Moreover, the storage elastic modulus in 110 Hz and 300 degreeC was 0.02 GPa, and the above-mentioned (8) 5% weight reduction | decrease temperature was 320 degreeC.

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

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

Claims (39)

The following ingredients:
(A) Polyamide precursor polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole that can be a polyoxazole precursor At least one resin selected from the group consisting of polybenzothiazole, and phenolic resin;
(B) a photosensitive agent; and (C) at least one selected from the group consisting of a polyfunctional (meth) acrylate and a low molecular weight imide compound having a molecular weight of less than 1000;
A photosensitive resin composition comprising:   The component (A) is a polyimide precursor consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, and polybenzothiazole. The photosensitive resin composition of Claim 1 which is at least 1 sort (s) of resin chosen.   The photosensitive resin composition 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. The component (A) is represented by the following general formula (A1):
{Wherein, X ₁ is a tetravalent organic group, Y ₁ is a divalent organic group, l is an integer of _{2 to} 150, and R ₁ and R ₂ are each independently A hydrogen atom or a monovalent organic group capable of radical polymerization. However, R ₁ and R ₂ are not simultaneously hydrogen atoms. }
And the component (C) is represented by the following general formula (C1):
{In the formula, R ₃ is a single bond, a hydrogen atom or a 1 to 3 valent organic group; R ₄ and R ₅ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 3 to 3 carbon atoms. 10 cycloalkyl groups, aryl groups, alkoxy groups or halogen atoms, and m is an integer of 1 or more. }
The photosensitive resin composition of any one of Claims 1-3 containing the maleimide represented by these. The component (A) is represented by the following general formula (A2):
{Wherein X ₂ is a tetravalent organic group, Y ² is a divalent organic group, n is an integer of 2 to 150, and R ₆ and R ₇ are each independently A hydrogen atom, the following general formula (A3):
_(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. However, R ₆ and R ₇ are not both hydrogen atoms at the same time. }
The photosensitive resin composition of any one of Claims 1-4 which is a polyimide precursor represented by these. The component (C) is represented by the following general formula (C2):
{In the formula, R ₁₁ represents a single bond, a hydrogen atom, or a 1-3 valent organic group; R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 3 to 3 carbon atoms. 10 cycloalkyl groups, aryl groups, alkoxy groups or halogen atoms, and q is an integer of 2-4. }
The photosensitive resin composition of any one of Claims 1-5 containing the maleimide represented by these.   The photosensitive resin composition of any one of Claims 1-6 whose said (B) component is an oxime system photoinitiator. The component (B) is the following components (B1) and (B2):
(B1) an oxime ester compound in which the 0.001 wt% solution has an i-ray absorbance of 0.15 to 0.5, and the 0.001 wt% solution has a g-ray absorbance and an h-ray absorbance of 0.2 or less; and (B2) An oxime ester compound in which the i-line absorbance of the 0.001 wt% solution is 0.1 or less and the g-ray absorbance or h-ray absorbance of the 0.001 wt% solution is 0.05 or more;
The photosensitive resin composition of any one of Claims 1-7 containing at least 1 sort (s) selected from the group which consists of.   The photosensitive resin composition according to claim 8, wherein an i-ray absorbance of a 0.001 wt% solution of the component (B1) is 0.15 to 0.35. The component (B1) is represented by the following general formulas (B11) and (B12):
{Wherein R ₁₄ is a C _{1 to} C ₁₀ fluorine-containing alkyl group, and R ₁₅ , R ₁₆ , and R ₁₇ are each independently a C _{1 to} C ₂₀ alkyl group, or a C _{3 to} C ₂₀ cycloalkyl _group, an aryl group of C 6 _{-C 20,} or an alkoxy group of _C 1 _{-C 20,} and r is an integer from 0 to 5. }
{In the formula, R ₁₈ is a C _{1 to} C ₃₀ divalent organic group, and R _{19 to} R ₂₆ are each independently a C _{1 to} C ₂₀ alkyl group or a C _{3 to} C ₂₀ cycloalkyl group. , an aryl group of _C 6 _{-C 20,} or an alkoxy group of _C 1 _{-C 20,} and s is an integer of 0 to 3. }
The photosensitive resin composition of Claim 8 or 9 containing at least 1 sort (s) selected from the group which consists of oxime ester compound represented by these. In addition to the above components (A) to (C),
(D) The following general formula (D1):
{Wherein R ₂₇ and R ₂₈ are C _{1 to} C ₄ alkyl groups, R ₂₉ is a C _{1 to} C ₆ divalent organic group, and R ₃₀ is composed of nitrogen, oxygen, and sulfur. An organic group of C _{1 to} C ₂₀ bonded to a carbonyl group by an atom selected from the group, t is an integer selected from 1, 2, and 3, and u is an integer selected from 0, 1, and 2. And t and u satisfy the relationship t + u = 3. }
The photosensitive resin composition of any one of Claims 1-10 containing the silicon containing compound represented by these. As the component (D), in addition to the silicon-containing compound represented by the formula (D1), the following general formula (D2):
{Wherein R ₃₁ and R ₃₂ are C _{1 to} C ₄ alkyl groups, R ₃₃ is a C _{1 to} C ₆ divalent organic group, and v is an integer selected from 1, 2, and 3 And w is an integer selected from 0, 1, and 2, and v and w satisfy the relationship of v + w = 3. }
The photosensitive resin composition of Claim 11 which further contains the silicon containing compound represented by these. In addition to the above components (A) to (C),
(E) The following general formula (E1):
{Wherein R ₃₄ is a C _{1 to} C ₂₀ organic group or silicon-containing organic group, and R ₃₅ is a C _{1 to} C ₂₀ bonded to a thiocarbonyl group by an atom selected from the group consisting of nitrogen, oxygen, and sulfur. Is an organic group. }
The photosensitive resin composition of any one of Claims 1-10 containing the sulfur containing compound represented by these. For 100 parts by mass of component (A),
0.1 to 20 parts by mass of the component (B); and 1 to 40 parts by mass of the component (C);
The photosensitive resin composition of any one of Claims 1-10 containing this. For 100 parts by mass of component (A),
0.1 to 20 parts by mass of the component (B); and 10 to 35 parts by mass of the component (C);
The photosensitive resin composition of any one of Claims 1-10 containing this. For 100 parts by mass of component (A),
0.1-20 parts by mass of the component (B);
1 to 40 parts by mass of the (C) component; and 0.1 to 20 parts by mass of the (D) component;
The photosensitive resin composition of Claim 11 or 12 containing this. For 100 parts by mass of component (A),
0.1-20 parts by mass of the component (B);
10 to 35 parts by mass of the component (C); and 0.1 to 20 parts by mass of the component (D);
The photosensitive resin composition of Claim 11 or 12 containing this. For 100 parts by mass of component (A),
0.1-20 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 of Claim 13 containing this. For 100 parts by mass of component (A),
0.1-20 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 of Claim 13 containing this. The following ingredients:
(AX) a photosensitive polyimide precursor;
The following (B1) and (B2) components:
(B1) an oxime ester compound in which the 0.001 wt% solution has an i-line absorbance of 0.15 to 0.5, and the 0.001 wt% solution has a g-line absorbance and an h-line absorbance of 0.2 or less, and (B2) An oxime ester compound in which the 0.001 wt% solution has an i-line absorbance of 0.1 or less and the 0.001 wt% solution has a g-line absorbance or h-line absorbance of 0.05 or more,
At least one selected from the group consisting of:
A photosensitive resin composition comprising: The (AX) component is represented by the following general formula (A2):
{Wherein X ₂ is a tetravalent organic group, Y ² is a divalent organic group, n is an integer of 2 to 150, and R ₆ and R ₇ are each independently A hydrogen atom, the following general formula (A3):
_(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. However, R ₆ and R ₇ are not both hydrogen atoms at the same time. }
The photosensitive resin composition of Claim 20 which is a polyimide precursor represented by these.   The photosensitive resin composition according to claim 20 or 21, wherein an i-ray absorbance of a 0.001 wt% solution of the component (B1) is 0.15 to 0.35. The component (B1) is represented by the following general formulas (B11) and (B12):
{Wherein R ₁₄ is a C _{1 to} C ₁₀ fluorine-containing alkyl group, and R ₁₅ , R ₁₆ , and R ₁₇ are each independently a C _{1 to} C ₂₀ alkyl group, or a C _{3 to} C ₂₀ cycloalkyl _group, an aryl group of C 6 _{-C 20,} or an alkoxy group of _C 1 _{-C 20,} and r is an integer from 0 to 5. }
{In the formula, R ₁₈ is a C _{1 to} C ₃₀ divalent organic group, and R _{19 to} R ₂₆ are each independently a C _{1 to} C ₂₀ alkyl group or a C _{3 to} C ₂₀ cycloalkyl group. , an aryl group of _C 6 _{-C 20,} or an alkoxy group of _C 1 _{-C 20,} and s is an integer of 0 to 3. }
The photosensitive resin composition of any one of Claims 20-22 containing at least 1 sort (s) selected from the group which consists of oxime ester compound represented by these.   The photosensitivity of any one of Claims 20-23 whose total content of the said (B1) component and (B2) component with respect to 100 mass parts of said (AX) components is 0.1-10 mass parts. Resin composition.   The photosensitive resin of any one of Claims 20-24 whose total content of the said (B1) component and (B2) component with respect to 100 mass parts of said (AX) components is 0.5-5 mass parts. Composition. The following ingredients:
(AY) polyimide precursor; and (D) the following general formula (D1):
{Wherein R ₂₇ and R ₂₈ are C _{1 to} C ₄ alkyl groups, R ₂₉ is a C _{1 to} C ₆ divalent organic group, and R ₃₀ is composed of nitrogen, oxygen, and sulfur. An organic group of C _{1 to} C ₂₀ bonded to a carbonyl group by an atom selected from the group, t is an integer selected from 1, 2, and 3, and u is an integer selected from 0, 1, and 2. And t and u satisfy the relationship t + u = 3. }
A silicon-containing compound represented by:
A resin composition comprising: As the component (D), in addition to the silicon-containing compound represented by the formula (D1), the following general formula (D2):
{Wherein R ₃₁ and R ₃₂ are C _{1 to} C ₄ alkyl groups, R ₃₃ is a C _{1 to} C ₆ divalent organic group, and v is an integer selected from 1, 2, and 3 And w is an integer selected from 0, 1, and 2, and v and w satisfy the relationship of v + w = 3. }
The resin composition according to claim 26, further comprising a silicon-containing compound represented by: The following ingredients:
(AY) polyimide precursor; and (E) the following general formula (E1):
{Wherein R ₃₄ is a C _{1 to} C ₂₀ organic group or silicon-containing organic group, and R ₃₅ is a C ₁ to C bonded to a thiocarbonyl group by an atom selected from the group consisting of nitrogen, oxygen, and sulfur. ₂₀ organic groups. }
A sulfur-containing compound represented by:
A resin composition comprising: The component (AY) is represented by the following general formula (A2):
{Wherein X ₂ is a tetravalent organic group, Y ² is a divalent organic group, n is an integer of 2 to 150, and R ₆ and R ₇ are each independently A hydrogen atom, the following general formula (A3):
_(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. However, R ₆ and R ₇ are not both hydrogen atoms at the same time. }
The resin composition of any one of Claims 26-28 which is a polyimide precursor represented by these. For 100 parts by mass of the (AY) component,
0.1 to 20 parts by mass of the component (D1); and 0.1 to 20 parts by mass of the component (D2);
The resin composition according to claim 27, comprising:   The resin composition of Claim 28 or 29 containing 0.1-20 mass parts of said (E) component with respect to 100 mass parts of said (AY) components.   (B) The resin composition according to any one of claims 26 to 31, further comprising a photosensitizer. below:
(1) The photosensitive resin composition according to any one of claims 1 to 25 or the resin composition according to claim 32 is applied on a substrate, and a photosensitive resin layer is formed on the substrate. Process,
(2) exposing the photosensitive resin layer;
(3) developing the photosensitive resin layer after the exposure to form a relief pattern;
(4) subjecting the relief pattern to a heat treatment to form a cured relief pattern;
A method for producing a cured relief pattern.   A semiconductor device provided with the hardening relief pattern obtained by the manufacturing method of Claim 33. The following ingredients:
(A) Polyamide precursor polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyhydroxyamide, polyaminoamide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole that can be a polyoxazole precursor At least one resin selected from the group consisting of polybenzothiazole, and phenolic resin,
Including
Crosslink density is 1.0 × 10 ⁻⁴ mol / cm ³ or more, 3.0 × 10 ⁻³ mol / cm ³ or less, and 5% weight loss temperature is 250 ° C. or more and 400 ° C. or less.
Resin film. The resin film according to claim 35, wherein the crosslink density is 3.0 × 10 ⁻⁴ mol / cm ³ or more and 2.0 × 10 ⁻³ mol / cm ³ or less.   The component (A) is a polyimide precursor consisting of polyamic acid, polyamic acid ester, polyamic acid salt, polyamic acid amide, polyamide, polyamideimide, polyimide, polybenzoxazole, polybenzimidazole, and polybenzothiazole. 37. The resin film according to claim 35 or 36, which is at least one selected resin.   The laminated body by which the resin film of any one of Claims 35-37 is laminated | stacked on the resin substrate whose glass transition temperature is 200 degrees C or less.   The laminated body by which the resin film of any one of Claims 35-37 is laminated | stacked on the resin substrate whose glass transition temperature is 250 degrees C or less.