JP2002356554A - Polyimide precursor and photosensitive resin composition using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new polyimide precursor to give an polyimide, without using a polyamidic acid having a problem in storage stability, and having no water-absorbing hydroxyl and carboxy group in a side chain, and to provide a new photosensitive resin composition using the precursor. SOLUTION: The polyimide precursor has polyamide units that is t-butylated in a polyamide acid position. Preferably, this polyimide precursor has polyimide units, and these units may be distributed in the same molecule or the polyamide acid position may contains the t-butylated polyamide acid and the polyimide units. This polyimide precursor is mixed with a photo-oxygen generating agent to form a positive-type photosensitive resin composition, and suitably used as a positive-type etching resist.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyimide precursor and a novel photosensitive resin composition using the same. More specifically, the present invention relates to a novel polyimide precursor having a polyamide moiety esterified with a t-butyl group, and a novel photosensitive resin composition containing, as essential components, the precursor and a photoacid generator that generates an acid upon irradiation with light. .

[0002]

2. Description of the Related Art Polyimide is excellent in heat resistance among various organic polymers, and is therefore widely used in the fields of space and aviation, the field of electronic communication, and the field of OA equipment. In particular, recently, it is desired not only to have excellent heat resistance but also to have various performances depending on the application.

[0003] For example, photosensitive polyimide obtained by imparting photosensitivity to polyimide is widely used for coating semiconductor chips. Most of conventional photosensitive polyimides are of a negative type in which a portion irradiated with light is insoluble in a developing solution.

[0004] However, as a more functional photosensitive heat-resistant resin, what is urgently developed in various fields is a heat-resistant positive-type photosensitive resin. The positive type has the following features as compared with the negative type.

(1) It is difficult for pinholes to come out. In the case of a negative type, if dust adheres, the dust is unexposed and a hole is formed and disconnection occurs. In the case of the positive type, there is no hole because the area under the dust is unexposed.

With the progress of high integration and fine wiring of LSIs, the influence of dust (particles) has increased.
If dust is attached to the exposure mask, the light does not pass under the dust even when irradiated with light. For this reason, in the case of a negative resist, the portion under the dust is the last exposed portion, and is dissolved and a hole is formed. Conversely, in the case of a positive resist, no hole is formed since the bottom of the dust is an unexposed portion.

When a circuit pattern is formed using a negative type mask, the circuit portion on the mask is outlined. If dust adheres to the white part, a hole is formed in the negative resist. As a result, when the conductor is etched with the negative resist superposed thereon, a hole is opened in the conductor circuit, and disconnection occurs.

When a positive type mask is used, the circuit portion is a light-shielding portion, and even if dust adheres, the pattern does not affect the pattern and no disconnection occurs. However, if dust adheres to a white portion between the circuits, the conductor in that portion remains to the end without being etched, and the adjacent circuit is short-circuited. However, removal and correction of the conductor in this portion can be easily performed.

(2) Forming a Positive Tapered Pattern When light is applied to the photosensitive resin, the light gradually becomes weaker and tapered as the resin layer becomes deeper. In the case of a positive photosensitive resin, a portion exposed to light is dissolved by a developing solution, so that a deeper resin layer forms a tapered hole. This is a hole (inverted triangle) of a normal taber which is ideal as a hole of the bonding pad portion.

On the other hand, in the case of a negative photosensitive resin, the opposite is true. The deeper the resin layer, the more the portion that is not exposed to light increases, and the portion that is dissolved by the developer becomes larger. As a result, the holes gradually become larger, and holes (equilateral triangles) of the inverted taber which are not preferable as the holes of the bonding pad portion are formed.

(3) High resolution Positive photosensitive resin is developed by resin dissolution. Therefore, the resolution is excellent, the contrast is high, and fine processing is possible.

On the other hand, the development of the negative photosensitive resin is of a swelling-peeling type. For this reason, the resin swells during development, the resin becomes thinner and thinner during curing, and the resolution is low, and the contrast is low.

(4) Work is safe and environmentally friendly Positive photosensitive resin can be developed with an alkaline aqueous solution, and the work is safe, environmentally friendly and less likely to cause pollution. The negative type uses a harmful organic solvent.

Due to these features, development of a heat-resistant positive-type photosensitive resin has been awaited, and active studies have been made.

Ohba et al. Of Toshiba have developed a resin in which an amino compound having a phenolic hydroxyl group is ion-bonded to a polyamic acid. A naphthoquinonediazide is added to this resin to form a positive photosensitive resin (J. Appl.
lym. Sci. , 58 [9], 1535-1542.
(1995)).

According to Nitto Denko, 1,4-
A resin to which a dihydroxypyridine derivative is added has been developed (Japanese Patent Application Laid-Open No. 7-179604). 1,4-Dihydropyridin to polyamic acid
The e derivative is mixed, and heat treatment is performed after light irradiation. At this time, in the exposed portion, Dihydropyridine changes to basic pyridine, the hydrophilicity increases, and the exposed portion dissolves.

These prior art references use amic acids. Amidic acid is unstable and is easily hydrolyzed by water in the air, and has a problem in storage stability of the photosensitive resin.

The following is an example in which an imidized resin is used to improve the storage stability.

Fukushima et al. Of Yokohama National University have developed a positive photosensitive polyimide obtained by adding naphthoquinonediazide to a soluble polyimide having a carboxyl group in the side chain (The 13th Annual Meeting of the Japan Institute of Electronics Packaging, 11th).
3 (1999)). The UV-irradiated polyimide has been developed with an aqueous solution of tetramethylammonium hydroxide. However, the alkali developability can be improved by adding a carboxyl group, but there are problems such as an increase in water absorption and an increase in ionic impurities due to the remaining carboxyl group. Another problem is that the sensitivity is as low as 1200 mJ / cm ² .

In addition, Akimoto et al. Of Toppan Printing have developed a positive photosensitive polyimide composition that does not swell the film during development, has excellent photosensitivity, resolution, and residual film properties, and does not require high heat treatment during final curing. (JP-A-11-84645). This composition comprises an already imidized soluble polyimide having a phenolic hydroxyl group in the side chain and a photosensitive diazoquinone compound. A hydroxyl group is necessary for a positive photosensitive resin using a diazoquinone compound,
Since it remains in the final cured product, it may cause an increase in water absorption and an increase in ionic impurities.

As described above, most of the conventional techniques introduce a water-absorbing hydroxyl group or carboxyl group into the side chain of the soluble polyimide. As described above, the water absorption rate is increased.
It was likely to cause an increase in ionic impurities.

[0022]

According to the present invention, the storage state before use does not take the structure of a polyamic acid having a problem in storage stability, and the final state is a water-absorbing hydroxyl group of a side chain. It is an object of the present invention to provide a novel polyimide precursor capable of providing a novel photosensitive resin composition which is an imide composition which does not require a carboxyl group or a carboxyl group, and a method for producing the same.

[0023]

Means for Solving the Problems As a result of intensive studies, the present inventors have made a new polyimide precursor having a specific structure, and a photoacid generator which generates an acid by irradiation with the precursor and an acid as essential components. It has been found that a predetermined purpose can be achieved by the novel photosensitive resin composition, and the present invention has been completed.

That is, the present invention relates to a unit represented by the following general formula (1):

[0025]

Embedded image (In the general formula (1), R ¹ represents a tetravalent organic group selected from the following group (1), and R ² represents a divalent organic group. R ¹ , R
² is the same or different between the units of the general formula (1). )

[0026]

Embedded image Provided is a polyimide precursor having a unit represented by the following general formula (2).

[0027]

Embedded image (In the general formula (2), R ³ represents a tetravalent organic group, and R ⁴ represents a divalent organic group. R ³ and R ⁴ are the same or different between the units of the general formula (2).) When the number of units of the general formula (1) and the number of units of the general formula (2) in the polyimide precursor are a and b, respectively, the relationship between a and b is preferably 0.01 ≦ a / (a + b) ≦ 0.99.

In another embodiment of the present invention, there is provided a polyimide precursor composition obtained by mixing a polyamide having a unit of the general formula (1) and a polyimide having a unit of the general formula (2). Is done.

Further, the above-mentioned polyimide precursor or polyimide precursor composition provides a photosensitive resin composition obtained by mixing a photoacid generator.

In one embodiment of the present invention, the general formula (1)
And a polyimide precursor having the unit of the general formula (2) are [(CH ₃ ) ₃ COC (＝ O)] ₂ R ¹ (COOH) ₂
And / or a dicarboxylic acid component containing a unit of the general formula (1) and a diamine component containing a unit of the general formula (2),
It is provided by a production method characterized by reacting. (R ¹ is the same as in the general formula (1).) [(CH ₃ ) ₃ COC (＝ O)] ₂ R ¹ (COOH)
It can also be provided by a production method characterized by reacting a dicarboxylic acid component containing a unit of ₂ and / or the general formula (1), an acid dianhydride, and dicyanate.
(R ¹ is the same as in the general formula (1).) Further, a diamine component containing a unit of the general formula (1) and an acid dianhydride represented by R ³ [(CO) ₂ O] _2. And / or an acid dianhydride component containing a unit of the general formula (2) to produce a polyamic acid, and imidating the polyamic acid moiety. (R ³ is the same as in the general formula (2).)

[0031]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The novel polyimide precursor of the present invention has a unit represented by the general formula (1).

[0032]

Embedded image (In the general formula (1), R ¹ represents a tetravalent organic group selected from the following group (1), and R ² represents a divalent organic group. R ¹ , R
² is the same or different between the units of the general formula (1). )

[0033]

Embedded image t-Butoxycarbonyl becomes a polyamic acid as represented by the following reaction formula (1) in the presence of a strong acid (H ⁺ ), and (CH ₃ ) ₂ C ＝ CH ₂ and H ⁺ are generated. When a photoacid generator that generates an acid by light irradiation is mixed with a polyimide precursor having a unit represented by the general formula (1), an acid is generated by light irradiation, and (CH ₃ ) _{2 is obtained} as shown in a reaction formula (1). C = CH ₂ is
The reaction formula (1) further evaporates into the atmosphere and is generated by H ^+.
The reaction is amplified, resulting in a chemically amplified photosensitive resist.

[0034]

Embedded image (R ¹ and R ² are the same as in the general formula (1).) Further, since the polyamic acid is generated, the light-irradiated portion is a positive photosensitive resin that dissolves in an alkaline aqueous solution.

The unit of the general formula (1) is imidized by heating as shown in the reaction formula (2) to become a heat-resistant resin. However, since the bulky group called t-butyl group is removed, the polyimide precursor consisting only of the general formula (1) causes a large volume shrinkage during imidization and a film reduction when a photosensitive resin is applied. , Undesirably causing shrinkage stress.

[0036]

Embedded image (R ¹ and R ² are the same as those in the general formula (1).) Therefore, a structure in which an amount of the site of the general formula (1) necessary for making the compound soluble in alkali is left, and the rest is imidized. By doing so, film loss can be reduced. Thus, in one embodiment of the present invention, the polyimide precursor has units of both general formula (1) and general formula (2).

[0037]

Embedded image (In the general formula (1), R ¹ represents a tetravalent organic group selected from the following group (1), and R ² represents a divalent organic group. R ¹ , R
² is the same or different between the units of the general formula (1). )

[0038]

Embedded image

[0039]

Embedded image (In the general formula (2), R ³ represents a tetravalent organic group and R ⁴ represents a divalent organic group. R ³ and R ⁴ are the same or different between the units of the general formula (2).) When the number of units of the general formula (1) and the number of units of the general formula (2) in the polyimide precursor are a and b, respectively, the relationship between a and b is 0.01 ≦ a / ( a + b)
≦ 0.99 (a is an integer of 1 or more, b is an integer of 1 or more) is preferable, and more preferably 0.05 ≦ a / (a
+ B) ≦ 0.95, more preferably 0.1 ≦ a /
(A + b) ≦ 0.9, particularly preferably 0.2 ≦ a /
(A + b) ≦ 0.8.

The average molecular weight per t-butyl group is
It is preferable to control the constitution of each monomer and the values of the above a and b so as to be in the range of 200 to 3000. The preferred average molecular weight per t-butyl group is 300 to 2000, more preferably 400 to 1
500. If it exceeds 3,000, alkali development may be difficult. In terms of alkali development, t
It is preferable that the average molecular weight per -butyl group is small, but if the average molecular weight per t-butyl group is too small, the average molecular weight per t-butyl group is 2.
00 or more is preferable.

A specific method for synthesizing a polyimide precursor having units of both general formulas (1) and (2) will be described.

First, [(CH ₃ ) ₃ COC (=
O)] A tetracarboxylic acid derivative represented by ₂ R ¹ (COOH) ₂ ; the following general formula (3) is synthesized.

[0043]

Embedded image (R ¹ is the same as in the general formula (1).) The tetracarboxylic acid derivative of the general formula (3) is obtained by reacting tetracarboxylic dianhydride with potassium t-butoxide in an aprotic solvent, It is obtained by recrystallization after neutralization with an acid.

Next, both the general formulas (1) and (2)
Method I for Synthesizing a Polyimide Precursor Having One Unit
To III are listed below. In these synthetic methods,
R¹, R ^Three, R^Two, R^FourIs the general formula (1) and the general formula
R of (2)¹, R^Three, R^Two, R^FourIs the same as Also,
R¹, R^Three, R^Two, R^FourIs the same for each unit
It may be different. That is, the synthesis method described below
In the formula, dicarbo represented by the general formula (3) is used as a monomer.
Acid, but one or more kinds can be used.
You. Other monomers: diamine, acid dianhydride, diiso
The same applies to cyanate and nitromonoamine.

However, the following description is made on the assumption that each monomer component is composed of one compound for convenience.
It does not limit the invention.

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image (Synthesis method I) Briefly describing this synthesis method, a dicarboxylic acid component containing a unit of the general formula (1)
A diamine component containing a unit of formula (1) in an aprotic polar solvent in the presence of a condensing agent, wherein the polyimide precursor having both units of general formulas (1) and (2) Can be synthesized.

The dicarboxylic acid component containing the unit of the above general formula (1) is a dicarboxylic acid of the general formula (3) and H ₂ N—R ² —NH ₂ (R ² is a compound represented by the general formula (1) The same is applied.), And the reaction is carried out in an aprotic polar solvent in the presence of a condensing agent. At this time, by making the number of moles of the dicarboxylic acid of the general formula (3) to be reacted larger than the number of moles of the diamine, an amide oligomer having a carboxyl group at both terminals is obtained.

The diamine component containing the unit represented by the general formula (2) is obtained by reacting the corresponding diamine with an acid dianhydride in an aprotic polar solvent, adding an azeotropic solvent such as toluene, and forming water to be formed. By actively discharging out of the system,
It is obtained by imidization. At this time, by making the number of moles of the diamine compound to be reacted excessively larger than the number of moles of the acid dianhydride, both ends become an imide oligomer having an amino group. The obtained diamine component (imide oligomer) containing the unit of the general formula (2) is represented by the following general formula (4).

[0051]

Embedded image Further, as shown in the following reaction formula (3), an acid dianhydride can be reacted with a diamine / nitromonoamine, imidized, and reduced to obtain a general formula (4).

[0052]

Embedded image By condensing the dicarboxylic acid component containing the unit of the general formula (1) and the diamine component containing the unit of the general formula (2) thus obtained, the general formulas (1) and (2) Can be synthesized, but a dicarboxylic acid of the general formula (3) may be used in place of the dicarboxylic acid component containing the unit of the general formula (1). Further, a dicarboxylic acid of the general formula (3) may be used in combination with a dicarboxylic acid component containing a unit of the general formula (1).

(Synthesis Method II) As shown in the reaction formula (4), the dicarboxylic acid of the general formula (3) is reacted with a diisocyanate to give an amic acid ester containing a unit of the general formula (1). Can be synthesized. Further, as shown in the reaction formula (5), a compound containing the unit of the general formula (2) can be synthesized by reacting an acid dianhydride with a diisocyanate.

Here, when the dicarboxylic acid, acid dianhydride and diisocyanate of the general formula (3) are added at once and reacted, a polyimide precursor having both units of the general formulas (1) and (2) is obtained. Can be synthesized. If the reaction temperature at that time is too high, there is a possibility that the amide ester site may be imidized, so the reaction temperature is preferably 200 ° C.
The control is performed as follows.

It is preferable to add a tertiary amine such as triethylamine as a catalyst to these reactions because the carboxylic acid is activated.

[0056]

Embedded image

[0057]

Embedded image Note that a dicarboxylic acid component containing the unit of the general formula (1) described in the synthesis method I may be used instead of the dicarboxylic acid of the general formula (3) depending on the purpose of controlling the sequence of the polyimide precursor or the like. . Further, a dicarboxylic acid component containing the unit of the general formula (1) described in the synthesis method I may be used in combination with the dicarboxylic acid of the general formula (3).

(Synthesis Method III) This synthesis method will be briefly described. A diamine component containing a unit of the general formula (1) and an acid dianhydride component containing a unit of the general formula (2) are combined with an aprotic polar solvent. The reaction is carried out in a polyamic acid and imidization is carried out by positively discharging water generated by adding an azeotropic solvent such as toluene to the outside of the system, or an acid anhydride such as acetic anhydride and a pyridine derivative or isoquinoline. This is a synthesis method in which imidization is carried out by reacting in the presence of a tertiary amine, and a polyimide precursor having both units of the general formulas (1) and (2) can be synthesized by this reaction.

The diamine component containing the unit of the above general formula (1) is a dicarboxylic acid of the general formula (3) and H ₂ N—R ² —NH ₂ (where R ² is the same as the general formula (1)). The reaction is carried out in an aprotic polar solvent in the presence of a condensing agent using a diamine represented by the formula:
At this time, by increasing the number of moles of the diamine reacted to the number of moles of the dicarboxylic acid of the general formula (3),
Both ends are amide oligomers having amino groups. For example,
When the molar ratio between the diamine and the dicarboxylic acid of the general formula (3) is 2: 1, the following general formula (5) is obtained. When 1 <diamine / general formula (3) <2, the following general formula is used. (6)
It becomes like. When this ratio exceeds 2, the diamine theoretically remains unreacted, but does not itself pose a problem.

[0060]

Embedded image (R ¹ and R ³ are the same as in the general formula (1).)

[0061]

Embedded image(R¹, R^ThreeIs the same as in the general formula (1). The acid dianhydride component containing the unit of the above general formula (2) is H
_TwoNR^Four-NH_Two(R^FourIs the same as in the general formula (2).
You. ) And R^Three[(CO)_TwoO]
_Two(R^ThreeIs the same as in the general formula (2). Acid)
Reaction of dianhydride with amidic acid in aprotic polar solvent
And add an azeotropic solvent such as toluene to remove the generated water out of the system.
It is obtained by imidization by positively discharging.
At this time, the mole number of the acid dianhydride to be reacted is
In excess of the number of moles of the product, both ends are acid
It becomes an imide oligomer of an anhydride.

When an acid dianhydride component containing a unit of the general formula (2) is obtained by the above-mentioned method, the acid anhydride rings at both terminals may be opened if the discharge of water out of the system is insufficient. However, a method in which an acid dianhydride and a diisocyanate are reacted in excess of an acid dianhydride to obtain an imide oligomer is preferable since imide oligomers having acid anhydrides at both terminals can be obtained because no water is generated.

The thus obtained diamine component containing the unit of the general formula (1) and the acid dianhydride component containing the unit of the general formula (2) are reacted in an aprotic polar solvent to obtain a polyamic acid. And water produced by adding an azeotropic solvent such as toluene is positively discharged to the outside of the system to imidize or in the presence of an acid anhydride such as acetic anhydride and a tertiary amine such as a pyridine derivative or isoquinoline. The polyimide precursor having both units of the general formula (1) and the general formula (2) can be synthesized by imidization by reacting with the above. The acid dianhydride component containing the unit of the general formula (2) And an acid dianhydride represented by R ³ [(CO) ₂ O] ₂ may be used. Further, an acid dianhydride represented by R ³ [(CO) ₂ O] ₂ may be used in combination with an acid dianhydride component containing a unit of the general formula (2).

Next, the condensing agent used for forming an amide bond with a dicarboxylic acid and a diamine represented by the general formula (3) will be described.

(PhO) ₃ P, (PhO) PCl ₂ , Ph
POCl ₂ , (C ₃ H ₇ ) P (O) O, POCl ₃ , SOC
l ₂ - triethylamine mixed _{system, Ph 3 P-C 2 Cl} 6 system,
SiCl ₄ , Me ₂ SiCl _{2 and the} like can be mentioned.
(Here, Ph represents a phenyl group and Me represents a methyl group.) (PhO) ₃ P, (PhO) PCl ₂ , Ph
POCl ₂ , (C ₃ H ₇ ) P (O) O, POCl _3, etc. react a carboxylic acid with an amine in an amide solvent such as N-methylpyrrolidone in the presence of a tertiary amine such as pyridine. This produces an amide bond.

When POCl ₃ or a phosphorus chloride of phosphorus trichloride is mixed with pyridine, the N-phosphonium salt formed effectively works as a condensing agent.

Further, the phosphoric ester or phosphoric amide shown in the following group (2) can also efficiently form an amide bond in an amide solvent containing a tertiary amine such as triethylamine under mild reaction conditions of 100 ° C. or less. Since it is formed, a high molecular weight polyamide can be synthesized.

[0068]

Embedded image (In the formula, R ⁵ is a monovalent organic group, and X represents O or S.) The method for synthesizing the copolymers of the general formulas (1) and (2) has been described above. In another embodiment of the invention,
Polyamide having units of general formula (1) and general formula (2)
Can be mixed to obtain a polyimide precursor composition. The mixing ratio of the polyamide having the unit of the general formula (1) and the polyimide having the unit of the general formula (2) is the same as in the case of the copolymerization, and the number of the units of the general formula (1) and the general formula (2) When the number of units is a and b, respectively, the relation between a and b is preferably 0.01 ≦ a / (a + b) ≦ 0.99 (a = 1 or more integer, b = 1 or more Represents an integer), more preferably 0.0
5 ≦ a / (a + b) ≦ 0.95, more preferably,
0.1 ≦ a / (a + b) ≦ 0.9, particularly preferably
The mixing ratio may be determined so that 0.2 ≦ a / (a + b) ≦ 0.8.

The polyamide having the unit of the general formula (1) is prepared by mixing the dicarboxylic acid of the general formula (3) with H ₂ N—R ² —N
It is obtained by reacting a diamine represented by H ₂ (R ² is the same as in the general formula (1)) with the above-described condensing agent in the presence of a tertiary amine in a substantially equimolar manner. Synthesis of polyimide having units of the general formula (2) is, R ³ as monomers
An acid dianhydride represented by [(CO) ₂ O] ₂ and H ₂ N—R ⁴ —
NH ₂ (R ⁴ is the same as in the general formula (2)) may be obtained by converting a diamine represented by the general formula (2) into a polyimide. As a method of mixing, it is desirable to dissolve and mix in a solvent, but it is also possible to apply heat and inject. In this case, it is preferable to perform the reaction at a temperature at which the polyamide moiety of the general formula (1) is not imidized.

The average molecular weight (weight average) of the polyimide precursor of the present invention is desirably 5,000 to 1,000,000. If the average molecular weight is too small, the polyimide composition after imidization also has a low molecular weight, and thus may be brittle. On the other hand, if the molecular weight is too large, the viscosity becomes too high and handling becomes difficult.

Further, various kinds of organic additives, inorganic fillers, or various kinds of reinforcing materials can be combined with the polyimide precursor.

Examples of the aprotic polar solvent used for the production reaction of the polyimide precursor include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, N, N-dimethylformamide, N, N-
Formamide solvents such as diethylformamide, N,
Acetamide solvents such as N-dimethylacetamide and N, N-diethylacetamide; pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone; or hexamethylphosphoramide, γ-butyrolactone, etc. It is desirable to use these alone or as a mixture, but it is also possible to partially use aromatic hydrocarbons such as xylene and toluene.

The acid dianhydride used for this polyimide precursor, that is, the acid dianhydride used for obtaining the unit of the general formula (2) is not particularly limited as long as it is an acid dianhydride. Butanetetracarboxylic dianhydride, 1,
2,3,4-cyclobutanetetracarboxylic dianhydride,
1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbonane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,
5-dioxotetrahydrofural) -3-methyl-3-
Cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5
Aliphatic or alicyclic tetracarboxylic dianhydride such as 6-tetracarboxylic dianhydride; pyromellitic acid, dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3 3,3 ', 4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'
-Biphenyl ether tetracarboxylic dianhydride, 3,
3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic acid Dianhydride, 4,4'-bis (3,
4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane Dianhydride, 3,3 ', 4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3', 4,4'-
Biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-
Phenylene-bis (triphenylphthalic acid) dianhydride,
Bis (triphenylphthalic acid) -4,4'-diphenylether dianhydride, bis (triphenylphthalic acid)-
Aromatic tetracarboxylic dianhydride such as 4,4'-diphenylmethane dianhydride; 1,3,3a, 4,5,9b-hexahydro-2,5-dioxo-3-furanyl) -naphtho [1,2 -C] furan-1,3-dione, 1,3,3
a, 4,5,9b-Hexahydro-5-methyl-5-
(Tetrahydro-2,5-dioxo-3-furanyl)-
Naphtho [1,2-c] furan-1,3-dione, 1,
3,3a, 4,5,9b-hexahydro-8-methyl-
5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione;
The following general formula (C);

[0074]

Embedded image (Wherein R ⁶ represents a divalent organic group having an aromatic ring, and R ⁷ and R ⁸ each represent a hydrogen atom or an alkyl group), and the following general formula (D);

[0075]

Embedded image (Wherein R ⁹ represents a divalent organic group having an aromatic ring, R ¹⁰
And R ¹¹ each represent a hydrogen atom or an alkyl group. And aliphatic tetracarboxylic dianhydrides having an aromatic ring such as the compounds represented by These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

The tetracarboxylic acid derivative having a t-butyl ester group used to obtain the unit of the general formula (1) is not particularly limited as long as it has a t-butyl ester group. )

[0077]

Embedded image (R ¹² represents —O—, —OC ₆ H ₄ —O—), or a compound represented by the following formula:

[0078]

Embedded image Is particularly preferred.

As the diamine used for the polyimide precursor, various diamines can be used. The diamine is not particularly limited as long as it is, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminophenylethane, 4,4'-diaminophenyl ether, 4,4 '-
Didiaminophenyl sulfide, 4,4'-didiaminophenyl sulfone, trifluoromethylphenylenediamine, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1-
(4'-aminophenyl) -1,3,3-trimethylindane, 4,4'-diamino-2,2'-bistrifluoromethylbiphenyl, 4,4'-diamino-3,3 '
-Dimethylbiphenyl, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 4,
4'-diaminobenzanilide, 3,5-diamino-
3'-trifluoromethylbenzanilide, 3,5-diamino-4'-trifluoromethylbenzanilide,
3,4'-diaminodiphenyl ether, 2,7-diaminofluorene, 2,2-bis (4-aminophenyl)
Hexafluoropropane, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4 '-Diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2 -Bis [4-
(4-aminophenoxy) phenyl] propane, 2,2
-Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) -biphenyl, 1,3'- Bis (4-aminophenoxy) benzene, 9,9-bis (4-aminophenyl)
Fluorene, 4,4 '-(p-phenyleneisopropylidene) bisaniline, 4,4'-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4-
(4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-bis [4
Aromatic diamines such as-(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl;
An aromatic diamine having two amino groups bonded to an aromatic ring such as diaminotetraphenylthiophene and a hetero atom other than a nitrogen atom of the amino group; 1,1-methaxylylenediamine, 1,3-propanediamine; Tetramethylenediamine, pentamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7 -Methanoindaniline methylenediamine, tricyclo [6,
2,1,0 ^2.7 ] -undecylenedimethyldiamine,
Aliphatic diamines and alicyclic diamines such as 4,4'-methylenebis (cyclohexylamine); the following general formula (E);

[0080]

Embedded image (Wherein R ¹³ represents —O—, —COO—, —OCO—, —C
It represents a divalent organic group selected from ONH- and -CO-, and R ¹⁴ represents a monovalent organic group having a steroid skeleton. A) monosubstituted phenylenediamine represented by the following general formula (8);

[0081]

Embedded image (R ¹⁵ represents a hydrocarbon group having 1 to 12 carbon atoms, y is 1 to
And z is an integer of 1 to 20. And the like. These diamine compounds can be used alone or in combination of two or more.

The acid generator used in the present invention will be described. Although it is not particularly limited as long as it generates an acid by light irradiation, a preferred example is exemplified. For example, as shown in the following group (3), a type generating sulfonic acid, an iodonium salt, a sulfonium salt, an onium salt and the like can be exemplified.

[0083]

Embedded image (R ¹⁶ is a methyl ethyl propyl group, R ¹⁷ is the following general formula (9);

[0084]

Embedded image R ¹⁸ is hydrogen / methoxy / methyl / dimethylamino / diethylamino; R ¹⁹ is hydrogen / methyl / t-
A butyl group, R ²⁰ represents hydrogen, methyl, t-butyl, phenoxy, phenyl, methoxy, and

[0085]

Embedded image The, R ²¹ is an O or S, X ^{- _{is, AsF 6 - · SbF 6 -}} ·
_{^{PF 6 - · CF 3 SO 3}} - · CF 3 CO 2 - · Cl - · Br - · B
F ₄ ^- a, Y represents a nitro group or a cyano group or hydrogen, m and n
Indicates 1 or 2. Also, diazonium salts represented by the group (4), bis (trichloromethyl) triazines represented by the groups (5) and (6), and compounds capable of forming a sulfone group represented by the group (7) may be used. is there. (Wherein R ²² and R ^24, a phenyl-dimethylamino group, diethylamino group, methoxy ethoxy diphenylamino group, a nitro group, a halogen, X ^{-
_{Is, AsF 6 - · SbF 6 -}} · PF 6 - · CF 3 SO 3 - · CF 3
_{^{CO 2 - · Cl - · Br}} - · BF 4 - · CH 3 C 6 H 4 SO 3 - ·
B (C ₆ H ₅ ) ₄ ^— , r is an integer of 1 to 3, n and p are 1 to
An integer of 5, R ²³ and R ^{25 each} represent a phenyl C1-C10 alkyl group. )

[0086]

Embedded image

[0087]

Embedded image

[0088]

Embedded image

[0089]

Embedded image In addition, naphthoquinonediazide may be partially used because it generates carboxylic acid by light and improves solubility in alkali.

The photoacid generator is contained as 0.3 to 20% by weight based on the polyimide precursor. If too much photoacid generator is used, dielectric properties and mechanical strength in the film,
In addition to deteriorating heat resistance, light transmittance is also poor, making it difficult to form a complete hole. However, if the amount used is extremely small, sufficient acid will not be present and the role as an acid generator will not be sufficiently exhibited, resulting in poor resolution.

The sensitivity can be improved by mixing these acid generators and sensitizers.

Preferred examples of the sensitizer include Michler's ketone, bis-4,4'-diethylaminobenzophenone,
Benzophenone, camphorquinone, benzyl, 4,
4'-dimethylaminobenzyl, 3,5-bis (diethylaminobenzylidene) -N-methyl-4-piperidone, 3,5-bis (dimethylaminobenzylidene) -N
-Methyl-4-piperidone, 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidone,
3,3'-carbonylbis (7-diethylamino) coumarin, riboflavin tetrabutyrate, 2-methyl-1
-[4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-dimethylthioxanthone,
2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 3,5-dimethylthioxanthone, 3,5-diisopropylthioxanthone, 1-phenyl-2- (ethoxycarbonyl) oxyiminopropan-1-one, benzoin ether, benzoin Isopropyl ether, benzanthrone, 5-nitroacenaphthene, 2-nitrofluorene, anthrone, 1,2-
Benzanthraquinone, 1-phenyl-5-mercapto-1H-tetrazole, thioxanthen-9-one,
0-thioxanthenone, 3-acetylindole, 2,
6-di (p-dimethylaminobenzal) -4-carboxycyclohexanone, 2,6-di (p-dimethylaminobenzal) -4-hydroxycyclohexanone, 2,6
-Di (p-diethylaminobenzal) -4-carboxycyclohexanone, 2,6-di (p-diethylaminobenzal) -4-hydroxycyclohexanone, 4,6-
Dimethyl-7-ethylaminocoumarin, 7-diethylamino-4-methylcoumarin, 7-diethylamino-3-
(1-methylbenzimidazolyl) coumarin, 3- (2
-Benzimidazolyl) -7-diethylaminocoumarin, 3- (2-benzothiazolyl) -7-diethylaminocoumarin, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl)
Quinoline, 4- (p-dimethylaminostyryl) quinoline, 2- (p-dimethylaminostyryl) zenzothiazole, 2- (p-dimethylaminostyryl) -3,3-
Examples include, but are not limited to, dimethyl-3H-indole.

The sensitizer is the polyimide precursor 10 of the present invention.
0.1 to 50 parts by weight, preferably 0.3 to 20 parts by weight, is added to 0 part by weight. If the amount is out of the range of 0.1 to 50 parts by weight, the sensitizing effect may not be obtained or the developability may be adversely affected. As the sensitizer, one type of compound may be used, or a mixture of several types may be used.

Further, a photopolymerization auxiliary may be separately contained. Examples of the photopolymerization auxiliary include 4-diethylaminoethyl benzoate, 4-dimethylaminoethyl benzoate, 4-diethylaminopropyl benzoate,
-Dimethylaminopropylbenzoate, 4-dimethylaminoisoamylbenzoate, N-phenylglycine, N-methyl-N-phenylglycine, N- (4-cyanophenyl) glycine, 4-dimethylaminobenzonitrile, ethylene glycol dithioglycolate, ethylene Glycol di (3-merbutopropionate),
Trimethylolpropane thioglycolate, trimethylolpropane tri (3-mercaptopropionate),
Pentaerythritol tetrathioglycolate, pentaerythritol tetra (3-mercaptopropionate), trimethylolethanetrithioglycolate, trimethylolpropanetrithioglycolate, trimethylolethanetri (3-mercaptopropionate),
Dipentaerythritol hexa (3-mercaptopropionate), thioglycolic acid, α-mercaptopropionic acid, t-butylperoxybenzoate, t-butylperoxymethoxybenzoate, t-butylperoxynitrobenzoate, t-butylperoxyethyl Benzoate, phenylisopropylperoxybenzoate, di-t-butyldiperoxyisophthalate, tri-t-butyltriperoxytrimellitate, tri-t-
Butyltriperoxytrimesitate, tetra-t-butyltetraperoxypyromellitate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 3,
3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3,4,4'-tetra (t
-Amyl peroxycarbonyl) benzophenone, 3,
3 ', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 2,6-di (p-azidobenzal) -4-hydroxycyclohexanone, 2,6-di (p-azidobenzal) -4-carboxycyclohexanone, 2,6-di (p-azidobenzal) -4-methoxycyclohexanone, 2,6-di (p-azidobenzal) -4-hydroxymethylcyclohexanone, 3,5
Di- (p-azidobenzal) -1-methyl-4-piperidone, 3,5-di (p-azidobenzal) -4-piperidone, 3,5-di (p-azibenzal) -N-acetyl-4-piperidone; 3,5-di (p-azidobenzal)
-N-methoxycarbonyl-4-piperidone, 2,6-
Di (p-azidobenzal) -4-hydroxycyclohexanone, 2,6-di (m-azidobenzal) -4-carboxycyclohexanone, 2,6-di (m-azidobenzal) -4-methoxycyclohexanone, 2,6-di ( m-azidobenzal) -4-hydroxymethylcyclohexanone, 3,5-di (m-azidobenzal) -N-
Methyl-4-piperidone, 3,5-di (m-azidobenzal) -4-piperidone, 3,5-di (m-azidobenzal) -N-acetyl-4-piperidone, 3,5-di (m-azidobenzal)- N-methoxycarbonyl-4
-Piperidone, 2,6-di (p-azidocinnamylidene) -4-hydroxycyclohexanone, 2,6-di (p-azidocinnamylidene) -4-carboxycyclohexanone, 2,6-di (p-azido) Cinnamiliden)
-4-cyclohexanone, 3,5-di (p-azidocinnamylidene) -N-methyl-4-piperidone, 4,4 '
-Diazido chalcone, 3,3 'diazido chalcone,
3,4'-diazidochalcone, 4,3'-diazidochalcone, 1,3-diphenyl-1,2,3-propanetrione-2- (o-acetyl) oxime, 1,3-diphenyl-1, 2,3-propanetrione-2- (on-
Propylcarbonyl) oxime, 1,3-diphenyl-
1,2,3-propanetrione-2- (o-methoxycarbonyl) oxime, 1,3-diphenyl-1,2,3
-Propanetrione-2- (o-ethoxycarbonyl)
Oxime, 1,3-diphenyl-1,2,3-propanetrione-2- (o-benzoyl) oxime, 1,3-
Diphenyl-1,2,3-propanetrione-2- (o
-Phenyloxycarbonyl) oxime, 1,3-bis (p-methylphenyl) -1,2,3-propanetrione-2- (o-benzoyl) oxime, 1,3-bis (p-methoxyphenyl) -1 , 2,3-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-
(P-methoxyphenyl) -3- (p-nitrophenyl) -1,2,3-propanetrione-2- (o-phenyloxycarbonyl) oxime can be used, but is not limited thereto.

When the photopolymerization aid is used, it is preferably used in an amount of 0.1 to 50 parts by weight, more preferably 0.3 to 20 parts by weight, based on 100 parts by weight of the polyimide precursor of the present invention. preferable. If the amount is out of the range of 0.1 to 50 parts by weight, the intended sensitizing effect may not be obtained, or may adversely affect the developability. In addition, one kind of compound may be used as the photopolymerization aid, or several kinds may be mixed.

The photosensitive resin composition according to the present invention can be manufactured and used in the form of a solution. Examples of the solvent include dimethyl sulfoxide, hexamethylphosphamide, dimethylacetamide, dimethylformamide,
N-methyl-2-pyrrolidone, gamma-butyrolactone, diglyme, butoxyethanol, propylene glycol methyl ethyl acetate (P
GMEA), but is not limited to a specific solvent. The solvent may be used by mixing two or more solvents in order to control the uniformity and thickness of the thin film and to improve the adhesive strength. The heat-resistant photoresist composition is manufactured so that its concentration is in the range of 0.1 to 70% by weight, and is used after being adjusted according to the thickness of the coating.

The formation of a thin film using the photosensitive resin composition can be performed by any of spin coating, bar coating, and doctor blade methods widely used in the electronics industry. The drying temperature for forming a thin film is suitably from 40 to 150C. If the drying temperature is extremely low, the drying time is prolonged. If the drying temperature is extremely high, thermal decomposition of the acid-sensitive group occurs, which is not desirable.

The exposure may be performed by using an exposure apparatus that emits visible light or ultraviolet light having a wavelength of 200 to 500 nm. It is preferable to use an exposure device equipped with a filter that exhibits a monochromatic wavelength. More advantageous in aspects. The invention is not limited to any particular equipment or exposure equipment.

The exposure time can be changed according to the experimental conditions. According to the present invention, when an ultraviolet exposure apparatus equipped with the used 365 nm filter is used, the exposure time is 5 to 5.
The exposure time can be changed up to 240 seconds, and the exposure time can be shortened by a more powerful exposure apparatus. The exposure energy is quantified by an energy meter, and the resolving power is confirmed by depth and width by a profile meter. The cross section of the thin film is confirmed by an electron microscope.

As the developing solution, an alkaline aqueous solution is used. Specifically, sodium hydroxide, potassium hydroxide,
Inorganic alkalis such as sodium silicate and ammonia;
Primary amines such as ethylamine and propylamine; secondary amines such as diethylamine and dipropylamine;
Tertiary amines such as trimethylamine and triethylamine; alcoholamines such as diethylethanolamine and triethanolamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxymethylammonium hydroxide, triethylhydroxymethylammonium hydroxide, trimethylhydroxyl Quaternary ammonium salts such as ethylammonium hydroxide; and the like.

Further, if necessary, a suitable amount of a water-soluble organic solvent such as methanol, ethanol, propanol or ethylene glycol, a surfactant, a storage stabilizer, a resin dissolution inhibitor or the like can be added to the above-mentioned alkaline aqueous solution.

[0102]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.

The evaluation of “film loss” in the examples was performed by the following method.

<Evaluation Method for Film Thinning>
It was dissolved in MF, applied to a 25 μm polyimide film (Apical NPI manufactured by Kaneka Chemical Co., Ltd.), and dried at 100 ° C. for 30 minutes to obtain a coating film having a thickness of about 10 μm. (This thickness was defined as the initial thickness.) The coating film was heated at 250 ° C. for 20 minutes to be imidized. The thickness at this time was defined as the thickness after imidization. The film reduction rate was calculated by the following equation. Film reduction rate (%) = [(initial thickness) − (thickness after imidization)] × 100 / (initial thickness) (Synthesis Example 1) 2,5-bis (t-butoxycarbonyl)
Synthesis of terephthalic acid 21.81 g (100 mmol) of pyromellitic dianhydride, 22.44 g (200 mmol) of potassium t-butoxy, and 300 ml of anhydrous tetrahydrofuran were placed in a reaction vessel, and refluxed and stirred for 24 hours under a nitrogen stream. . After cooling, the reaction solution was filtered and dried to obtain a white solid. This solid was dissolved in 300 ml of water, and hydrochloric acid was added until the pH reached about 4, while checking with a pH test paper. The deposited precipitate is separated by filtration and dried, and ethanol: water = 1: 1 (volume ratio).
To obtain 16.1 g (44% yield) of 2,5-bis (t-butoxycarbonyl) terephthalic acid. 1H-NMR (CDCl ₃ + DMS
O-d ₆ ): δ 1.60 (s; 18H, t-butyl),
7.80 (s; 2H, benzene ring) (Synthesis Example 2) Synthesis of 2,2'-bis (t-butoxycarbonyl) -4,4'-oxydibenzoic acid 4,4'-oxydiphthalic dianhydride 31.02 g (1
00 mmol), potassium t-butoxide 22.44 g
(200 mmol), anhydrous tetrahydrofuran 350 m
was placed in a reaction vessel and refluxed and stirred under a nitrogen stream for 24 hours. After cooling, the reaction solution was filtered and dried to obtain a white solid. This solid was dissolved in 300 ml of water, and hydrochloric acid was added until the pH reached about 4, while checking with a pH test paper. The deposited precipitate was separated by filtration, dried and recrystallized from acetonitrile to obtain 18.34 g (yield: 40%) of 2,2'-bis (t-butoxycarbonyl) -4,4'-oxydibenzoic acid. Was. 1H-NMR (CDCl ₃ +
_{DMSO-d 6): δ1.50 (} s; 18H, t- butyl), 6.8-7.8 (m; 6H, benzene ring) (Synthesis Example 3) diphenyliodonium di um 9,10-dimethoxy anthracene -2 -Preparation of sulfonate sodium 9,10-dimethoxyanthracene-2-
It was obtained by taking equimolar amounts of sulfonate and diphenyliodium chloride and recrystallizing with hot water.

Synthesis Example 4 p-Nitrobenzyl 9,10
Synthesis of -Dimethoxyanthracene-2-sulfonate The synthesis method is described in Macromolecules, 4788-
4795, 23 (1990).

Example 1 (A) 7.33 g (20 mmol) of 2,5-bis (t-butoxycarbonyl) terephthalic acid obtained in Synthesis Example 1, phosphoric acid amide 2,3-dihydro manufactured by Tokyo Kasei −
15.32 g (40 mmol) of diphenyl 2-thioxo-3-benzoxazolylphosphonate, 2,2'-ditrifluoromethylbenzidine manufactured by Wakayama Seika
68 g (40 mmol), N-methylpyrrolidone 80
g and 4.05 g (40 mmol) of triethylamine were placed in a reaction vessel and stirred at room temperature for 24 hours.

(B) 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4,4'-
5.30 g (30 mmol) of tetracarboxylic dianhydride, 2,2'-ditrifluoromethylbenzidine
57 g (10 mmol) and 80 g of N-methylpyrrolidone (hereinafter NMP) were placed in a reaction vessel and stirred at room temperature for 1 hour. The reaction solution of (A) was added to the container of (B), and the mixture was stirred at room temperature for 4 hours to obtain a viscous polyamic acid solution. In this solution, 12.22 g (120 mmol) of acetic anhydride, 26.2 g (260 mmol) of β-picoline,
50 g of N-methylpyrrolidone was added and the mixture was added at room temperature for 2 hours,
Stirring was performed at 00 ° C. for 1 hour. This solution was added to methanol 1
The mixture was poured into 500 ml, and the precipitated resin was pulverized by a mixer, washed and dried with Soxhlet using methanol as a solvent, to obtain 40.5 g of a novel polyimide precursor of the present invention. Weight average molecular weight 100,000. The film reduction rate was 15%. The structure is represented by the following formula.

[0108]

Embedded image 0.5 g of the photoacid generator synthesized in Synthesis Example 4 / 4.5 g of the new polyimide precursor were dissolved in 95 g of N-methylpyrrolidone to obtain a new photosensitive resin composition of the present invention.

A spin coat was applied to a silicon wafer (5 inches) and dried at 100 ° C. for 30 minutes.
A coating film having a thickness of 5 μm was obtained. After covering with a mask, after exposure (100 mJ / cm ² ), development and washing with 2% KOH aqueous solution, drying at 80 ° C. for 10 minutes and 300 ° C. for 10 minutes,
A line / space pattern with a pitch of μm could be drawn.

Similarly, 0.5 g of the photoacid generator / 4.5 g of the new polyimide precursor was dissolved in 20 g of N-methylpyrrolidone, applied to a copper foil, and fixed together with the copper foil to a pin frame.
30 minutes / 150 ° C 30 minutes / 300 ° C 15 minutes / 400 degrees 3
It was dried for a minute, removed from the pin frame, the copper foil was removed by etching, washed with water and dried to obtain a 25 μm thick polyimide film. The thermal decomposition onset temperature of this polyimide film is
At 550 degrees, the coefficient of thermal expansion was 3 ppm.

The structure of the final imide composition is represented by the following formula.

[0112]

Embedded image (Example 2) 2,2'-hexafluoropropylidene-
9.68 g (25 mmol) of 4,4'-diphthalic dianhydride, 8.8 of 2,5-diaminobenzotrifluoride
1 g (50 mmol) and 70 g of NMP were placed in a reaction vessel and stirred at room temperature for 5 hours. Then, 50 ml of toluene was added and heated to 150 ° C. Water generated by azeotropic distillation was positively discharged out of the system by a Dean-Stark distillation tube, and heating was continued until no more water was precipitated. After the toluene was distilled off, the temperature was returned to room temperature.

To the reaction solution, 11.46 g (25 mmol) of 2,2'-bis (t-butoxycarbonyl) -4,4'-oxydibenzoic acid of Synthesis Example 2 and phosphoric amide 2,3 manufactured by Tokyo Kasei -Dihydro-2-thioxo-
Diphenyl 3-benzoxazolylphosphonate 1
9.15 g (50 mmol), triethylamine 5.0
6 g (50 mmol) and 100 g of NMP were added and reacted at room temperature for 24 hours. The obtained viscous liquid was poured into methanol, and the precipitated resin component was pulverized with a mixer, and then washed and dried with Soxhlet using methanol as a solvent.
27.5 g of the novel polyimide precursor of the present invention was obtained. Weight average molecular weight 90,000. The film reduction rate was 20%. The structure is represented by the following formula.

[0114]

Embedded image 0.5 g of the photoacid generator synthesized in Synthesis Example 4 / 4.5 g of the new polyimide precursor were dissolved in 95 g of N-methylpyrrolidone to obtain a new photosensitive resin composition of the present invention.

By spin coating, the composition was applied to a silicon wafer (5 inches) and dried at 100 ° C. for 30 minutes.
A coating film having a thickness of 5 μm was obtained. After covering with a mask, after exposure (100 mJ / cm ² ), development and washing with 2% KOH aqueous solution, drying at 80 ° C. for 10 minutes and 300 ° C. for 10 minutes,
A line / space pattern with a pitch of μm could be drawn.

Similarly, 0.5 g of the photoacid generator / 4.5 g of the new polyimide precursor was dissolved in 20 g of N-methylpyrrolidone, applied to a copper foil, and fixed together with the copper foil to a pin frame.
30 minutes / 150 ° C 30 minutes / 300 ° C 15 minutes / 400 degrees 3
It was dried for a minute, removed from the pin frame, the copper foil was removed by etching, washed with water and dried to obtain a 25 μm thick polyimide film. The thermal decomposition onset temperature of this polyimide film is
At 550 degrees, the coefficient of thermal expansion was 5 ppm.

The structure of the final imide composition is represented by the following formula.

[0118]

Embedded image (Example 3) (C) 7.33 g (20 mmol) of 2,5-bis (t-butoxycarbonyl) terephthalic acid obtained in Synthesis Example 1, phosphoric acid amide 2,3-dihydro- manufactured by Tokyo Chemical Industry
15.32 g (40 mmol) of diphenyl 2-thioxo-3-benzoxazolylphosphonate, 2,2′-ditrifluoromethylbenzine 5.69 manufactured by Wakayama Seika
g (20 mmol), 80 g of N-methylpyrrolidone and 4.05 g (40 mmol) of triethylamine were placed in a reaction vessel and stirred at room temperature for 24 hours to obtain a viscous solution. This solution is poured into 500 ml of methanol,
The precipitated resin was pulverized by a mixer, washed with Soxhlet using methanol as a solvent, and dried to obtain 12.0 g of a polyimide precursor. Weight average molecular weight 80,000. The film reduction rate of this polyimide precursor was 35%. The structure is represented by the following formula.

[0119]

Embedded image (D) 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4,4'-tetracarboxylic dianhydride 17.30 g (30 mmol), 2,2'
19.71 g of ditrifluoromethylbenzidine (30
Mmol), N-methylpyrrolidone (NMP) 12
0 g was placed in a reaction vessel and stirred at room temperature for 4 hours to obtain a viscous polyamic acid solution. Acetic anhydride 10.2 was added to this solution.
g (100 mmol), 5 g (50 mmol) of β-picoline, and 50 g of N-methylpyrrolidone, and the mixture was stirred at room temperature for 2 hours and at 100 ° C. for 1 hour. This solution was poured into 1500 ml of methanol, and the precipitated resin was pulverized with a mixer, washed with Soxhlet using methanol as a solvent, and dried to obtain 35 g of polyimide. Weight average molecular weight 120,000. The structure is represented by the following formula.

[0120]

Embedded image Dissolving 0.5 g of the photoacid generator synthesized in Synthesis Example 4 / 2.0 g of the polyimide precursor (C) /2.5 g of the polyimide (D) in 95 g of N-methylpyrrolidone to obtain a new photosensitive resin of the present invention The composition was used. The film reduction rate of this composition is 12%
Met.

By spin coating, a silicon wafer (5 inches) was applied and dried at 100 ° C. for 30 minutes.
A coating film having a thickness of 5 μm was obtained. After covering with a mask, after exposure (100 mJ / cm ² ), development and washing with 2% KOH aqueous solution, drying at 80 ° C. for 10 minutes and 300 ° C. for 10 minutes,
A line / space pattern with a pitch of μm could be drawn.

Similarly, 0.5 g of the photoacid generator / 4.5 g of the new polyimide precursor were dissolved in 20 g of N-methylpyrrolidone, applied to a copper foil, and fixed together with the copper foil to a pin frame.
30 minutes / 150 ° C 30 minutes / 300 ° C 15 minutes / 400 degrees 3
It was dried for a minute, removed from the pin frame, the copper foil was removed by etching, washed with water and dried to obtain a 25 μm thick polyimide film. The thermal decomposition onset temperature of this polyimide film is
At 550 degrees, the coefficient of thermal expansion was 6 ppm.

The final imide structure is represented by the following formula.

[0124]

Embedded image

[0125]

The present invention can provide a polyimide precursor capable of providing an imide composition having a low water absorption because a hydroxyl group or a carboxyl group of a side chain is not essential, and a novel photosensitive resin composition using the same. . Further, since the polyamic acid moiety is t-butylated, the storage stability is excellent. Further, the change in volume due to the imidation of the amic acid ester moiety is small, and for example, the film can be prevented from being reduced in the case of a coating film.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA02 AA10 AA11 AC01 AD03 BE00 BE10 BG00 CB25 CB41 FA41 4J043 PA04 PA08 PA19 PC075 QB31 RA05 RA35 SA06 SA52 SA54 SA61 SA63 SA72 SA82 SB03 TA12 TA14 TA22 TA32 TB02 UA06132 UA121 UA142 UB011 UB021 UB122 UB132 UB321 UB331 VA022 XA16 YA06 ZA23 ZB22

Claims (7)

[Claims] 1. A unit represented by the following general formula (1): (In the general formula (1), R ¹ represents a tetravalent organic group selected from the following group (1), and R ² represents a divalent organic group. R ¹ , R
² is the same or different between the units of the general formula (1). ) A polyimide precursor having a unit represented by the following general formula (2). Embedded image (In the general formula (2), R ³ represents a tetravalent organic group and R ⁴ represents a divalent organic group. R ³ and R ⁴ are the same or different between the units of the general formula (2).) 2. When the number of units of the general formula (1) and the number of units of the general formula (2) in the polyimide precursor are a and b, respectively, the relationship between a and b is 0. 2. The polyimide precursor according to claim 1, wherein 0.01≤a / (a + b) ≤0.99. 3. A polyimide precursor composition obtained by mixing a polyamide having a unit of the general formula (1) with a polyimide having a unit of the general formula (2). 4. A photosensitive resin composition comprising a mixture of the polyimide precursor or the polyimide precursor composition according to claim 1 and a photoacid generator. 5. The method for producing a polyimide precursor according to claim 1, wherein [(CH ₃ ) ₃ COC (=
O)] ₂ R ¹ (COOH) ₂ and / or general formula (1)
A method for producing a polyimide precursor, comprising reacting a dicarboxylic acid component containing a unit of formula (I) with a diamine component containing a unit of formula (2). (R ¹ is the same as in the general formula (1).) 6. The method for producing a polyimide precursor according to claim 1, wherein [(CH ₃ ) ₃ COC (=
O)] ₂ R ¹ (COOH) ₂ and / or general formula (1)
A method for producing a polyimide precursor, comprising reacting a dicarboxylic acid component containing the following unit, an acid dianhydride, and dicyanate. (R ¹ is the same as in the general formula (1).) 7. The method for producing a polyimide precursor according to claim 1, wherein the diamine component contains a unit represented by the general formula (1) and R ³ [(CO) ₂ O] _2. A method for producing a polyimide precursor, comprising reacting an acid dianhydride and / or an acid dianhydride component containing a unit of the general formula (2) to produce a polyamic acid, and imidating the polyamic acid site. . (R ³ is the same as in the general formula (2).)