JP2010196041A - Poly (amic acid-imide) resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a poly (amic acid-imide) resin having excellent transparency, enabling chemical modification and which does not practically generate siloxane outgas, in which a polyimide resin derived from the resin has excellent flexibility. <P>SOLUTION: The poly (amic acid-imide) resin obtained by subjecting a combination of a specific tetracarboxylic acid dianhydride, a specific aromatic diamine and a specific polyoxyalkylene diamine to copolymerization reaction is used. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a poly (amic acid-imide) resin.

In recent years, the importance of polyimide resin as a heat-resistant insulating material in electronic devices is increasing. Polyimide resin has not only excellent heat resistance, but also chemical resistance, radiation resistance, electrical insulation, excellent mechanical properties, etc., so it can be used for flexible printed circuit (FPC) substrates, tape automation bonding ( TAB) base materials, chip-on-film (COF) base materials, protective films for semiconductor elements, interlayer insulating films for integrated circuits, and the like, are currently widely used.

Conventionally known polyimide resins have a rigid molecular chain and thus have excellent heat resistance, but lack flexibility and tend to be inferior in flexibility. In order to improve these performances, solvent-soluble polyimide resins using polysiloxane diamine as a raw material have been proposed as diamine components (Patent Documents 1 to 4). However, although this polyimide resin has improved flexibility and low moisture absorption, it has problems such as generation of a large amount of siloxane-based outgas at high temperatures. Siloxane-based outgas causes defects in the polyimide resin coating or causes a decrease in adhesion between the polyimide resin and the substrate. Furthermore, most semiconductor components such as substrates are silicon-based inorganic materials, and siloxane-based outgas is not preferable because it has a high affinity with these and easily reacts to cause a decrease in reliability as a semiconductor.

In addition, a block copolymerized polyimide resin containing a polyoxyalkylene chain has been proposed as a thermoplastic elastomer having relatively excellent flexibility and thermal stability (Patent Document 5). However, the thermoplastic elastomer has a low glass transition temperature (Tg) of about −80 ° C. and can be used as a substitute for rubber, but is required to have heat resistance in the fields of electrical and electronic materials and optical materials. As a material, it was not satisfactory.

On the other hand, in recent years, research and development of photosensitive polyimide resin (or its precursor) has been actively carried out, which greatly shortens the process of forming a fine pattern of a polyimide resin film, but polyimide having both flexibility and high transparency. If photosensitivity can be further imparted to the resin, a material extremely useful in the industrial field can be provided.

Furthermore, recently, in consideration of the environment, the importance of a positive photosensitive polyimide resin precursor for alkaline aqueous solution development is increasing compared to a negative type in which development is performed with an organic solvent.

If an alkali-soluble polyimide resin precursor (polyamic acid) is used, a positive fine pattern can be formed in principle. However, polyamic acid is too soluble in tetramethylammonium hydroxide aqueous solution, sodium carbonate aqueous solution, sodium hydrogen carbonate aqueous solution, sodium hydroxide aqueous solution and the like generally used as an alkali developer for semiconductor resists. The effect of addition is insufficient, and in many cases, it is difficult to form a clear pattern. This is because the carboxyl group in the polyamic acid is easily dissociated (low pKa value). For this reason, it is necessary to apply some chemical modification to the structure of the polyamic acid to control the solubility in an alkaline aqueous solution.

In addition to controlling the solubility of the polyamic acid, an important point is the transparency of the polyamic acid film. When exposure is performed with i-line (365 nm) of a high-pressure mercury lamp, if the transmittance of the film at this wavelength is not sufficiently high, the irradiation light is shielded by the polyamic acid itself, and it is difficult for the light to reach the photosensitive agent. In extreme cases, the photoreaction of the photosensitizer is hindered, and pattern formation becomes impossible.

Generally used all aromatic polyimide resins have a characteristic that the transparency of the film is extremely low because they have a strong electron absorption transition from the ultraviolet region to the visible light region. This is due to intramolecular conjugation through aromatic groups in the polyimide chain and intramolecular / intermolecular charge transfer interaction (Non-Patent Document 1).

As a countermeasure, it has been proposed that either one or both of a tetracarboxylic dianhydride component and a diamine component be a non-aromatic monomer (Patent Document 6). By this method, the intramolecular conjugation and the charge transfer interaction are hindered, so that improvement of the transparency of the polyimide resin from the ultraviolet region to the visible light region is expected.
Industrially available non-aromatic tetracarboxylic dianhydrides include bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 1,2 , 4,5-cyclohexanetetracarboxylic dianhydride.
However, since these monomers have low polymerization reactivity of their polyamic acid, there is a tendency that a high molecular weight polyimide resin is difficult to obtain. Therefore, there is a possibility that sufficient mechanical strength cannot be obtained.

On the other hand, when an alicyclic diamine is used as a non-aromatic diamine, the polyimide resin precursor first forms an amine salt at the initial stage of production of the polyamic acid, and the solubility in the reaction solvent decreases. Therefore, an error occurs in the charged molar ratio, and the degree of polymerization of the polyamic acid is difficult to increase. As a result, it becomes difficult to obtain a high molecular weight polyimide resin. Even if the polymerization reaction of the polyamic acid is continued as it is, the solubility of the amine salt in the reaction solvent is low, so that a long reaction time is required, and the productivity and reproducibility may be reduced.
For example, when a polyimide resin precursor is produced from pyromellitic dianhydride and trans-1,4-diaminocyclohexane, a very strong amine salt is formed, so that no polyimide resin precursor (polyamic acid) is produced.
Such a phenomenon is caused by the fact that the basicity of the alicyclic diamine is extremely higher than the basicity of the aromatic diamine, which leads to difficulty in producing a high molecular weight polyimide resin using the alicyclic diamine.

Japanese Patent Laid-Open No. 5-331285 Japanese Patent Laid-Open No. 9-40777 Japanese Patent Laid-Open No. 10-218993 JP 2000-103848 A JP-A-5-262875 JP 2000-204245 A

Prog. Polym. Sci., 26, 259 (2001)

An object of the present invention is a poly (amide acid-imide) resin, which is a polyimide resin precursor that has excellent transparency, can be chemically modified, and does not substantially generate siloxane-based outgas. An object of the present invention is to provide a poly (amide acid-imide) resin in which a polyimide resin derived from the resin has excellent flexibility.

As a result of intensive studies to achieve the above-mentioned problems, the present inventor has found that a poly (amide acid-imide) resin of a specific tetracarboxylic dianhydride, a specific aromatic diamine and a polyoxyalkylene diamine. However, it has been found that it is excellent in transparency, can be chemically modified, does not substantially generate siloxane-based outgas, and that the polyimide resin derived from the resin also has excellent flexibility. Based on this finding, the present invention has been completed.

  That is, the present invention provides the following items.

［式中、Ｒ^１及びＲ^２は同一又は異なって、それぞれ水素原子又はメチル基を表す。］
一般式（２）

［式中、Ｍは―Ｏ―、―ＳＯ_２―、―Ｃ（ＣＨ_３）_２―、―Ｃ（ＣＦ_３）_２―から選ばれる二価の基を表し、同一であっても異なっていてもよい。ｎは、１〜５の整数を表す。］
一般式（３）

［式中、Ｒ^３は水素原子又はメチル基を表す。Ｘ及びＺは、それぞれエチレン基又はプロピレン基を表す。Ｙは、炭素数２〜４の直鎖状若しくは分岐鎖状のアルキレン基を表す。ａ、ｂ及びｃは、同一又は異なって、それぞれ０〜５０の整数を表し、且つ、ａ＋ｂ＋ｃの合計が２〜５０の整数である。］ [Claim 1]
In the presence of a reaction solvent, the tetracarboxylic dianhydride (A) represented by the following general formula (1), the aromatic diamine (B) represented by the following general formula (2), and the following general formula (3) A polyoxyalkylenediamine (C)
(A) Poly (amic acid-imide) resin obtained by copolymerizing the component 100 at a charged molar ratio in which the sum of the components (B) and (C) is in the range of 80 to 125.
General formula (1)

[Wherein, R ¹ and R ² are the same or different and each represents a hydrogen atom or a methyl group. ]
General formula (2)

[Wherein, M represents a divalent group selected from —O—, —SO ₂ —, —C (CH ₃ ) ₂ —, and —C (CF ₃ ) ₂ —, which may be the same or different. Also good. n represents an integer of 1 to 5. ]
General formula (3)

[Wherein R ³ represents a hydrogen atom or a methyl group. X and Z each represent an ethylene group or a propylene group. Y represents a linear or branched alkylene group having 2 to 4 carbon atoms. a, b and c are the same or different and each represents an integer of 0 to 50, and the sum of a + b + c is an integer of 2 to 50. ]

[Section 2]
A poly (amide acid-imide) resin obtained by copolymerizing a tetracarboxylic dianhydride (A), an aromatic diamine (B) and a polyoxyalkylene diamine (C),
The total charge molar ratio is in the range of 80 to 125 with respect to the component (A) 100 and the sum of the component (B) and the component (C), and
In the step (I) and the step (I) in which an imidization copolymerization reaction is performed in the presence of a reaction solvent at a charged molar ratio in the range of (A) component 100, (B) components 15 to 90, and (C) components 0 to 25. A step of subjecting the obtained reaction solution to an amidation copolymerization reaction at a charged molar ratio in the range of (B) component 0 to 25 and (C) component 10 to 85 with respect to (A) component in step (I) ( II),
Item 2. A poly (amide acid-imide) resin according to item 1.

[Section 3]
Item 3. The poly (amic acid-imide) resin according to Item 1 or 2, wherein the molar ratio of the component (B) to the component (C) is in the range of (B) :( C) = 15: 85 to 90:10.

[Claim 4]
The number average molecular weight is 3,000 to 100,000, the weight average molecular weight is 6,000 to 200,000, and the acid value is 5 to 250 mgKOH / g, (Amic acid-imide) resin.

[Section 5]
Item 5. A poly (amide acid-imide) varnish containing the poly (amide acid-imide) resin according to any one of Items 1 to 4 and an organic solvent.

[Claim 6]
Item 5. A photosensitive resin composition containing the poly (amidic acid-imide) resin according to any one of Items 1 to 4 and a photosensitive agent, or the poly (amic acid-imide) varnish according to Item 5 and a photosensitive agent. (Or positive photosensitive resin composition).

[Claim 7]
Photosensitizer is diarylsulfonium salt, triarylsulfonium salt, dialkylphenacylsulfonium salt, diaryliodonium salt, aryldiazonium salt, aromatic tetracarboxylic acid ester, aromatic sulfonic acid ester, nitrobenzyl ester, aromatic N-oxyimide Item 7. The photosensitive resin composition according to Item 6, which is at least one photosensitive agent selected from the group consisting of sulfonates, aromatic sulfamides, benzoquinone diazide sulfonic acid esters and naphthoquinone diazide sulfonic acid esters (or positive photosensitive resin). Resin composition).

[Section 8]
Item 8. The photosensitive resin composition (or positive photosensitive resin composition) according to Item 6 or 7, wherein the photosensitive agent contains 1 to 100 parts by weight with respect to 100 parts by weight of the poly (amic acid-imide) resin.

［式中、Ｒ^１及びＲ^２は同一又は異なって、それぞれ水素原子又はメチル基を表す。］
一般式（２）

［式中、Ｍは―Ｏ―、―ＳＯ_２―、―Ｃ（ＣＨ_３）_２―、―Ｃ（ＣＦ_３）_２―から選ばれる二価の基を表し、同一であっても異なっていてもよい。ｎは、１〜５の整数を表す。］
一般式（３）

［式中、Ｒ^３は水素原子又はメチル基を表す。Ｘ及びＺは、それぞれエチレン基又はプロピレン基を表す。Ｙは、炭素数２〜４の直鎖状若しくは分岐鎖状のアルキレン基を表す。ａ、ｂ及びｃは、同一又は異なって、それぞれ０〜５０の整数を表し、且つ、ａ＋ｂ＋ｃの合計が２〜５０の整数である。］ [Claim 9]
In the presence of a reaction solvent, the tetracarboxylic dianhydride (A) represented by the following general formula (1), the aromatic diamine (B) represented by the following general formula (2), and the following general formula (3) A poly (alkylamido-imide) resin obtained by copolymerization reaction with polyoxyalkylenediamine (C),
The total charged molar ratio is a charged molar ratio in which the total of the component (B) and the component (C) is in the range of 80 to 125 with respect to the component (A) 100, and
The reaction solution obtained in the step (I) in which the imidization polymerization reaction is performed at a charged molar ratio in the range of (A) component 100, (B) components 15 to 90, and (C) components 0 to 25, and the reaction solution obtained in step (I) Step (II) in which the amidation polymerization reaction is carried out at a charged molar ratio in the range of (B) component 0 to 25 and (C) component 10 to 85 with respect to component (A) in step (I),
A process for producing a poly (amic acid-imide) resin comprising:
General formula (1)

[Wherein, R ¹ and R ² are the same or different and each represents a hydrogen atom or a methyl group. ]
General formula (2)

[Wherein, M represents a divalent group selected from —O—, —SO ₂ —, —C (CH ₃ ) ₂ —, and —C (CF ₃ ) ₂ —, which may be the same or different. Also good. n represents an integer of 1 to 5. ]
General formula (3)

[Wherein R ³ represents a hydrogen atom or a methyl group. X and Z each represent an ethylene group or a propylene group. Y represents a linear or branched alkylene group having 2 to 4 carbon atoms. a, b and c are the same or different and each represents an integer of 0 to 50, and the sum of a + b + c is an integer of 2 to 50. ]

[Section 10]
Item 10. The method for producing a poly (amic acid-imide) resin according to Item 9, wherein the molar ratio of the component (B) to the component (C) is in the range of (B) :( C) = 15: 85 to 90:10. .

[Section 11]
Item 11. The poly (amic acid) according to Item 9 or 10, wherein the number average molecular weight is 3,000 to 100,000, the weight average molecular weight is 6,000 to 200,000, and the acid value is 5 to 250 mgKOH / g. -Imide) Resin production method.

[Claim 12]
Item 5. A method of using the poly (amide acid-imide) resin according to any one of Items 1 to 4 for photosensitive resin use.

According to the present invention, it is possible to obtain a poly (amide acid-imide) resin that is a polyimide resin precursor that is excellent in transparency, can be chemically modified, and does not substantially generate siloxane-based outgas. The polyimide resin derived from the poly (amic acid-imide) resin has excellent flexibility. Furthermore, using the poly (amic acid-imide) resin, alkali development is possible, and the cured product (film or film) is excellent in flexibility and can form a cured product having a fine pattern forming ability. The resin composition can be provided and can be used for various electronic devices such as a protective film for a semiconductor element, a liquid crystal alignment film, and an interlayer insulating film for an integrated circuit.

<Poly (amic acid-imide) resin>
In the presence of a reaction solvent, the poly (amide acid-imide) resin according to the present invention comprises a tetracarboxylic dianhydride (A) represented by the general formula (1) and an aromatic diamine represented by the general formula (2). Preparation of (B) and the polyoxyalkylenediamine (C) represented by the general formula (3) with respect to the component (A) 100 such that the sum of the components (B) and (C) is in the range of 80 to 125. It can be obtained by carrying out a copolymerization reaction at a molar ratio.

(Tetracarboxylic dianhydride: component (A))
The tetracarboxylic dianhydride (A) represented by the general formula (1), which is a constituent component of the poly (amidic acid-imide) resin according to the present invention, is not particularly limited, and is a commercially available product or a conventionally known production method. What is obtained can be used.

  Specifically, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 4- (2,5-dioxy Oxotetrahydrofuran-3-yl) -4-methyl-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -7 -Methyl-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride. Examples of commercially available products include “Ricacid TDA-100 (product name)” (4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydro manufactured by Shin Nippon Chemical Co., Ltd. Naphthalene-1,2-dicarboxylic dianhydride).

  Moreover, tetracarboxylic dianhydride can be used by substituting a part of the tetracarboxylic dianhydride with another tetracarboxylic dianhydride as long as the effects of the present invention are not hindered. Other tetracarboxylic dianhydrides include aromatic tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides, or alicyclic tetracarboxylic dianhydrides.

Specifically, examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 4,4′-oxydiphthalic anhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride. 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4- Furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfone Anhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4, 4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, 1,2-ethylenebis (anhydrotrimellitate), 1,3-propylenebis (anhydrotritriate) Meritate), 1,4-tetramethylene bis (anhydro trimellitate), 1,5-pentamethylene bis (anhydro trimellitate), , 6-hexamethylene-bis (anhydrotrimellitate), 1,3-phenylene bis (anhydrotrimellitate), 1,4-phenylene bis (anhydrotrimellitate) and the like.

Examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride and 1,2,4,5-pentanetetracarboxylic dianhydride.

  In addition, as alicyclic tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbonane-2-acetic acid dianhydride 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, bicyclo [2.2.1] -heptane-2,3,5 6-tetracarboxylic dianhydride, bicyclo [2.2.2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] -octene- 2,3,5,6-te Rakarubon dianhydride and the like.

  Said other tetracarboxylic dianhydride can be used for the said copolymerization reaction individually or in mixture of 2 or more types.

  When a part of the tetracarboxylic dianhydride is used in place of the above-mentioned other tetracarboxylic dianhydrides, the amount used is preferably 10 with respect to the number of moles of all tetracarboxylic dianhydrides. A mol% or less, more preferably 5 mol% or less, particularly 1 mol% or less is recommended.

In the present specification and claims, the component (A) is described in the form of “tetracarboxylic dianhydride”, but various derivatives shown below can be used for the imidization reaction instead. . For example, tetracarboxylic acid which is a derivative of the tetracarboxylic dianhydride, an acid chloride of the tetracarboxylic acid, an ester of the tetracarboxylic acid and a lower alcohol having 1 to 4 carbon atoms, and the like can be given.

(Aromatic diamine: component (B))
The aromatic diamine (B) represented by the general formula (2), which is a constituent component of the poly (amic acid-imide) resin according to the present invention, is not particularly limited and can be obtained by a commercially available product or a conventionally known production method. Can be used.

Among the aromatic diamines represented by the general formula (2), M is preferably a divalent group selected from —O—, —C (CH ₃ ) ₂ —, and —C (CF ₃ ) ₂ —. And may be the same or different, and n is an integer of 1 to 3, and more preferably, M represents —O— and n represents 1 or Those that are 2 are recommended.

Specifically, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4 -(3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2 , 2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene and the like are exemplified. Among these, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (3-aminophenoxy) benzene, 1, because of particularly excellent balance between flexibility and transparency, 3-Bis (3- (3-aminophenoxy) phenoxy) benzene is recommended.

Said aromatic diamine can be used for a copolymerization reaction individually or in mixture of 2 or more types.

(Polyoxyalkylenediamine: (C) component)
The polyoxyalkylene diamine (C) represented by the general formula (3), which is a constituent component of the poly (amic acid-imide) resin according to the present invention, is not particularly limited and can be obtained by a commercially available product or a conventionally known production method. Things can be used.

Among the polyoxyalkylene diamines, R ³ is hydrogen, X is an ethylene group, a is 2 to 50 and b, c is a diamine, R ³ is a methyl group, X is a propylene group, and a is 2 to 2. 50 and b, c is 0 diamine, R ³ is methyl group, X is propylene group, Y is ethylene group and a + b is 2 to 50 and c is 0 diamine, R ³ is hydrogen, X is ethylene group and Z is Z diamine tetramethylene group and a + b is 2 to 50 and c is 0, ^{R 3} is a methyl group, X is a diamine of the propylene group in Z is tetramethylene group, and a + b is 2 to 50 and c is 0, ^{R 3} is hydrogen, X and Z are ethylene groups, Y is a trimethylene group and a + b + c is a diamine having 2 to 50, R ³ is hydrogen, X and Z are ethylene groups, Y is a tetramethylene group and a + b + c is a diamine having 2 to 50, and R ³ is methyl Base X, Z is a diamine of the Y propylene group is an ethylene group, and a + b + c 2-50, ^{R 3} is a methyl group, X, Z is Y propylene group tetramethylene group and a + b + c is recommended diamine 2-50 .

More preferably, R ³ is hydrogen and X is an ethylene group and a is 5 to 40 and b, c is a diamine of 0, R ³ is a methyl group, X is a propylene group, and a is 5 to 40 and b. c is 0 diamine, R ³ is methyl group, X is propylene group, Y is ethylene group and a + b is 5 to 40 and c is 0 diamine, R ³ is hydrogen, X is ethylene group and Y is tetramethylene group and a + b is 5 to 40 and c is 0 diamine, R ³ is methyl group, X is propylene group, Y is tetramethylene group, a + b is 5 to 40 and c is 0 diamine, R ³ is hydrogen, X is ethylene group Wherein Y is a trimethylene group and a + b + c is a diamine of 5 to 40, R ³ is hydrogen, X is an ethylene group, Y is a tetramethylene group and a + b + c is a diamine of 5 to 40, R ³ is a methyl group, and X and Z are propylene groups And Y is Echi Diamine emissions groups and a + b + c is 5-40, ^{R 3} is a methyl group, X, Z is Y propylene group tetramethylene group and a + b + c is recommended diamine 5-40.

More preferably, R ³ is hydrogen and X is an ethylene group and a is 10 to 30 and b, c is a diamine 0, R ³ is a methyl group, X is a propylene group, a is 10 to 35, and b and c are 0 diamine, R ³ is a methyl group, X is a propylene group, Y is an ethylene group, and a + b is 10 to 30 and c is 0 diamine, R ³ is hydrogen, X is an ethylene group, Y is a tetramethylene group, and a + b is 10-30 and diamines c is 0, ^{R 3} is a methyl group, X is a diamine tetramethylene group propylene group Y is and a + b is 10 to 30 and c is 0, ^{R 3} is hydrogen, X, Z is an ethylene group Wherein Y is a trimethylene group and a + b + c is a diamine of 10 to 30, R ³ is hydrogen, X and Z are ethylene groups, Y is a tetramethylene group and a + b + c is a diamine of 10 to 30, R ³ is a methyl group, and X and Z are Professional Diamine in Ren group Y is an ethylene group, and a + b + c 10-30, ^{R 3} is a methyl group, X, Z is Y propylene group tetramethylene group and a + b + c is recommended diamine 10-30.

Examples of such commercially available polyoxyalkylene diamines include the Jeffamine series manufactured by Huntsman. Specifically, Jeffamine D-230 [R ³ : methyl group, X: propylene group, a = 2 to 3, b = c = 0], Jeffamine D-400 [R ³ : methyl group, X: propylene Group, a = 5 to 6, b = c = 0], Jeffamine D-2000 [R ³ : methyl group, X: propylene group, a = 33, b = c = 0], Jeffamine HK-511 (XTJ -511) ^{[R 3:} methyl group, X, Z: propylene group, Y: an ethylene group, a + c = 1.2, b = 2.0], Jeffamine XTJ-500 (ED-600) [R 3: methyl Group, X, Z: propylene group, Y: ethylene group, a + c = 3.6, b = 9.0], Jeffamine XTJ-501 (ED-900) [R ³ : methyl group, X, Z: propylene group , Y: ethylene group, a + c = 6.0, b = 12.5], Jeffermi XTJ-502 (ED-2003) [R 3: methyl group, X, Z: propylene group, Y: an ethylene group, a + c = 6.0, b = 39], Jeffamine XTJ-504 (EDR-148) [R ^3: a hydrogen atom, Y: an ethylene group, a = 2, b = c = 0], Jeffamine XTJ-533 ^{[R 3:} methyl group, X, Z: propylene group, Y: butylene, a + c = 23.0 , b = 11.0], Jeffamine XTJ-536 ^{[R 3:} methyl group, X, Z: propylene group, Y: butylene, a + c = 16.0, b = 17.0], Jeffamine XTJ-542 [R ³ : methyl group, X, Z: propylene group, Y: tetramethylene group, a + c = 5.0, b = 9.0] and the like. Among these, Jeffermin D-400, Jeffermin D-2000, Jeffermin XTJ-500 (ED-600), Jeffermin XTJ-501 (ED-900), Jeffermin XTJ-502 (ED-2003), Jeffermin XTJ -533, Jeffermin XTJ-536, and Jeffermin XTJ-542 are preferable. In particular, Jeffermin D-2000, Jeffermin XTJ-501 (ED-900), Jeffermin XTJ-502 (ED-2003), Jeffermin XTJ- 542, Jeffamine XTJ-533, Jeffamine XTJ-536 are recommended.

Said polyoxyalkylene diamine can be used individually or in mixture of 2 or more types.

  The molar ratio of each component according to the present invention is the tetracarboxylic dianhydride (A) represented by the general formula (1), the aromatic diamine (B) represented by the general formula (2), and the general formula (3). The polyoxyalkylenediamine (C) represented by the formula (A) is a charged molar ratio in which the total of the components (B) and (C) is in the range of 80 to 125 with respect to the component (A) 100, The range is 90 to 110, and the range 95 to 105 is particularly recommended. The poly (amide acid-imide) resin of the present invention obtained in this range is excellent in the mechanical properties of the polyimide resin derived from the resin.

The molar ratio of the aromatic diamine (B) to the polyoxyalkylene diamine (C) is preferably in the range of (B) :( C) = 15: 85 to 90:10, more preferably (B ) :( C) = 15: 85 to 70:30, particularly (B) :( C) = 15: 85 to 60:40 is recommended. The poly (amic acid-imide) resin obtained in this range is excellent in transparency.

Other diamines can be used as the aromatic diamine and polyoxyalkylene diamine as long as the effects of the present invention are not impaired.

For example, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminobiphenyl, 9,9-bis (3-aminophenyl) fluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4 ′ -Diamino-3,3'5,5'-tetramethyldiphenylmethane, 4,4'-diamino-3,3'5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3'5,5 ' -Tetrapropyldiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3 '-Diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphe Aromatic sulfides such as sulfides, 3,3′-diaminodiphenyl sulfide, 1,4-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diaminodicyclohexylethane, 4,4′-diaminodicyclohexylpropane Bisaminomethylcyclohexane, diaminobicyclo [2.2.1] heptane, bis (aminomethyl) -bicyclo [2.2.1] heptane, ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, octamethylenediamine, Nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, octamethylenediamine, 2-methylpentamethylenediamine, 2-methyl-2,4-pentanediamine, 2,2-dimethylpropane-1,3- Amine, 2,2,4-trimethyl hexamethylene diamine, cycloaliphatic diamines containing an aliphatic diamine or alicyclic skeleton such 2,4,4-trimethylhexamethylene diamine.

  Said other diamine can be used for the said copolymerization reaction individually or in mixture of 2 or more types.

  When these other diamines are used, the amount used is preferably 10 mol% or less, more preferably 5 mol% or less, and particularly preferably 1 mol% or less, based on the total diamine.

In addition, aromatic diamines and polyoxyalkylene diamines can be used as long as the effects of the present invention can be obtained with respect to compounds obtained by converting amino groups to isocyanate groups or silylated compounds in order to improve reactivity.

<Copolymerization reaction>
The reaction method of the copolymerization reaction is not particularly limited as long as the target poly (amide acid-imide) resin can be produced, and a known reaction method can be used.

  Examples of the reaction method include a one-step process reaction method and a two-step process reaction method.

Specific examples of the one-step process reaction method include a reaction solvent, a tetracarboxylic dianhydride (A) component, an aromatic diamine (B) component, and a polyoxyalkylene diamine (C) component, Then, a charge molar ratio in which the sum of the component (B) and the component (C) is in the range of 80 to 125 is charged into the reactor and stirred at room temperature to 80 ° C. for 0.5 to 30 hours, and then the reaction of the imidation polymerization reaction. The method of performing reaction until it becomes a predetermined acid value at temperature is illustrated.

Specific examples of the two-step process reaction method include [Example i] Process (I): A predetermined amount of the component (A), the component (B), and the reaction solvent are charged in a reactor, and the temperature is from 0.5 to 80 ° C. at room temperature to 80 ° C. After stirring for 30 hours, an imidization polymerization reaction is performed at the reaction temperature of the imidation polymerization reaction, and the mixture is cooled to room temperature or lower. Step (II): A method in which a predetermined amount of the component (C) is charged into the reaction solution obtained in Step (I) and an amidation polymerization reaction is performed at 0 to 80 ° C. for 0.5 to 30 hours, [Example ii] Step (I): A predetermined amount of the component (A), a predetermined amount or a predetermined amount of the component (B), a predetermined amount of the component (C) and the reaction solvent are charged into the reactor, and the temperature is from room temperature to 80 ° C. After stirring for 0.5 to 30 hours, an imidization polymerization reaction is performed at the reaction temperature of the imidation polymerization reaction, and the mixture is cooled to room temperature or lower. Step (II): A method in which the remaining component (B) and component (C) are charged into the reaction solution obtained in step (I), and an amidation polymerization reaction is performed at 0 to 80 ° C. for 0.5 to 30 hours, Etc. are exemplified.

As the charge molar ratio of the two-step process reaction method, the total charge molar ratio is a charge molar ratio in which the total of the component (B) and the component (C) is in the range of 80 to 125 with respect to the component (A) 100. And it is preferable that the charging molar ratio of the step (I) is an imidation polymerization reaction at a charging molar ratio in the range of (A) component 100, (B) components 15 to 90, and (C) components 0 to 25. Preferably, the imidization polymerization is carried out at a charged molar ratio in the range of (B) components 20 to 80 and (C) components 0 to 20, more preferably in the range of (B) components 25 to 70 and (C) components 0 to 15. It is recommended to react. The charge molar ratio of step (II) is amidation polymerization with the charge molar ratio in the range of component (B) 0-25 and component (C) 10-85 with respect to component (A) in step (I). The reaction is preferably carried out, more preferably in the range of (B) component 0 to 20 and (C) component 20 to 80, and still more preferably in the range of (B) component 0 to 15 and (C) component 30 to 70. It is recommended that the amidation polymerization reaction be performed in a molar ratio.

Among the above production methods, the reaction method of the two-step process reaction method is recommended.

  The reaction temperature of the imidation polymerization reaction is usually 120 to 250 ° C, preferably 160 to 190 ° C.

  Although the reaction time of the imidation polymerization reaction depends on the type of substrate, the charging ratio, the substrate concentration, and the like, it is usually preferably about 2 to 10 hours after the start of the distillation of the produced water. When reaction time is too short, the tendency for imidation ratio to become low is recognized. If the reaction time is too long, the reaction system may partially cause a thermal crosslinking reaction to thicken the reaction system or form a gel-like material, or the reaction system may be colored due to thermal degradation of the reaction solvent. .

  In the imidation polymerization reaction, it is preferable to perform the reaction using a Dean Stark apparatus or the like while removing water generated during production. By performing such an operation, the degree of polymerization and the imidization rate can be further increased. At this time, it is recommended to use a liquid or a gas body accompanied with water for the purpose of efficiently removing generated water. The accompanying liquid or gas body is generally called a reflux liquid, an azeotropic agent, an accompanying agent or an accompanying gas.

  Examples of the reflux liquid include benzene, toluene, xylene, ethylbenzene, tetralin, cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, and mixtures thereof. These reflux solutions are usually used in an amount of 5 to 25% by weight based on the reaction solvent. The addition time is not particularly limited, and may be added to the reaction system from the time when the reaction solvent is charged, or may be added immediately before the imidation polymerization reaction.

  Moreover, 0-80 degreeC is preferable, as for the reaction temperature of the amidation polymerization reaction of process (II) of a two-step process reaction method, More preferably, 10-60 degreeC, Especially 20-50 degreeC is recommended.

  The inside of the reaction system is desirably an inert gas atmosphere from the viewpoint of preventing coloration and safety of the reaction system. Usually, a method is used in which the inside of the reaction system is replaced with an inert gas, and the inert gas is circulated during the reaction. Examples of the inert gas include nitrogen and argon.

(Reaction solvent)
The reaction solvent used in the copolymerization reaction according to the present invention may be any reaction solvent as long as it does not inhibit the copolymerization reaction and can dissolve the resulting poly (amidic acid-imide) resin.

As the organic solvent, an aprotic polar solvent is preferably used. Specifically, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, hexahexane Methyl phosphate triamide, 1,3-dimethylimidazolidinone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, cyclohexanone, cyclopentanone, γ-butyrolactone, methyl propylene glycol acetate, methyl ethylene glycol acetate, butyl propylene glycol acetate, methyl benzoate , Ethyl benzoate, isophorone, ethylene glycol diacetate, diethylene glycol butyl ether acetate, ethylene glycol monobutyl ether acetate Over DOO, propylene glycol diacetate, diethylene aminoglutethimide glycol ethyl ether acetate, dipropylene glycol methyl ether acetate and the like, it may be used alone or as a mixed system. Of these, N-methyl-2-pyrrolidone, γ-butyrolactone, and triethylene glycol dimethyl ether are particularly preferred from the viewpoint of polymerizability and viscosity stability.

  The amount of the reaction solvent used may be an amount that can dissolve the poly (amide acid-imide) resin to be produced. It is recommended that the concentration of the specific poly (amic acid-imide) resin is adjusted to preferably 5 to 50% by weight, more preferably 10 to 45% by weight, and further preferably 15 to 40% by weight. Is done.

  The reaction solvent may be the same as or different from the organic solvent constituting the poly (amic acid-imide) varnish according to the present invention, but is preferably the same in consideration of the complexity of the solvent replacement operation.

In addition, in this invention, in the range which does not impair the effect of this invention, end cap agents, such as monofunctional acid anhydride and amine, can be used together for the purpose of heat resistance, adhesive improvement, molecular weight control, etc. Specific examples of the end cap agent include phthalic anhydride, maleic anhydride, nadic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, citraconic anhydride, itaconic anhydride, 3-methylhexahydro as acid anhydrides. Phthalic anhydride, 4-methylhexahydrophthalic anhydride, 1-methylnorbornane-2, 3-dicarboxylic anhydride, 5-methylnorbornane-2, 3-dicarboxylic acid partial water, norbornane-2, 3-dicarboxylic acid Examples of amines such as anhydrides include aniline, methylaniline, allylamine, and cyclohexylamine.

The molecular weight of the poly (amide acid-imide) resin of the present invention is not particularly limited, but the number average molecular weight is 3,000 to 100,000 in terms of excellent balance of solvent solubility, mechanical strength, and thermal properties. 000, more preferably 4,000 to 50,000, particularly preferably 5,000 to 35,000 is recommended, and the weight average molecular weight is preferably 6,000 to 200,000, more preferably A range of 8,000 to 100,000, particularly preferably 10,000 to 50,000 is recommended. This range is a range having a degree of polymerization that can give a molded product. The molecular weight is a value measured by the method described in the Examples section below.

  The polydispersity of the poly (amic acid-imide) resin of the present invention is not particularly limited, but as the polydispersity in terms of excellent balance of solvent solubility, mechanical strength, and adhesion to the substrate, 1.0-20, more preferably 1.2-15, particularly preferably 1.5-10 is recommended.

As an index of the carboxyl group content of the poly (amic acid-imide) resin of the present invention, the acid value is preferably 5 to 250 mgKOH / g, more preferably 30 to 150 mgKOH, from the viewpoint of the balance between solvent solubility and thermal stability. A range of / g is recommended. In addition, an acid value is a value measured by the method as described in the item of the below-mentioned Example.

  The poly (amide acid-imide) resin of the present invention has a number average molecular weight of 3,000 to 100,000, a weight average molecular weight of 6,000 to 200,000, and an acid value of 5 to 250 mgKOH / g. More preferably, the number average molecular weight is 4,000 to 50,000, the weight average molecular weight is 8,000 to 100,000, and the acid value is 30 to 150 mgKOH / g. Of 5,000 to 35,000, a weight average molecular weight of 10,000 to 50,000, and an acid value of 30 to 150 mgKOH / g are recommended.

As the transparency of the poly (amic acid-imide) resin of the present invention, the transmittance at 365 nm (i-line) with a film thickness of 20 μm is preferably 50% or more, more preferably 65% or more. This range is a range having particularly excellent transparency. In addition, the transmittance | permeability is a value measured by the method as described in the term of the below-mentioned Example.

Since the poly (amic acid-imide) resin of the present invention is finally used as a polyimide resin, the performance as a polyimide resin is also important. As performance required as a polyimide resin, flexibility and heat resistance under use conditions are required. As the evaluation method, it can be evaluated by the glass transition temperature (Tg). As a glass transition temperature, the range of 35-120 degreeC is preferable from the point which is excellent in the softness | flexibility and heat resistance balance, More preferably, it is the range of 40-110 degreeC, The range of 50-100 degreeC is especially recommended. . When Tg is lower than 35 ° C., there is a high possibility that a problem arises in heat resistance under the use conditions of the polyimide resin, and when Tg is higher than 120 ° C., a tendency to be inferior in flexibility is seen, which is not preferable. In addition, Tg is a value measured by the method as described in the item of the below-mentioned Example.

<Poly (amic acid-imide) varnish>
The poly (amic acid-imide) varnish of the present invention contains the present poly (amic acid-imide) resin and an organic solvent.

  As a method for preparing a poly (amide acid-imide) varnish, (i) a method in which a reaction solvent solution of a poly (amide acid-imide) resin obtained by a copolymerization reaction is directly used as a poly (amide acid-imide) varnish, (Ii) A poly (amide acid-imide) resin isolated from a reaction solvent solution of the poly (amide acid-imide) resin obtained by the copolymerization reaction, and then isolated in a desired organic solvent And a method of obtaining a poly (amidic acid-imide) varnish by dissolving the resin.

  The solution viscosity of the poly (amic acid-imide) varnish is preferably 0.1 to 50 Pa · s, more preferably 0.5 to 20 Pa · s (measurement conditions; B-type viscometer, resin concentration 30% by weight, 25 ° C. ) Is recommended. It is desirable that the viscosity is appropriately adjusted during the production of the varnish.

The concentration of the poly (amic acid-imide) resin in the poly (amic acid-imide) varnish is preferably 5 to 50% by weight, more preferably 10 to 45% by weight, and even more preferably 15 to 40% by weight. It is recommended to adjust as follows.

  The organic solvent is not particularly limited as long as it is an organic solvent capable of dissolving the polyimide resin according to the present invention, and specific examples include those exemplified as the reaction solvent. Among these, N-methyl-2-pyrrolidone, γ-butyrolactone, and triethylene glycol dimethyl ether are particularly recommended.

<Photosensitive resin composition>
The photosensitive resin composition of this invention is obtained by mix | blending a photosensitive agent (photoacid generator) with the said poly (amide acid-imide) resin or poly (amide acid-imide) varnish.

  The photosensitizer used in the present invention is not particularly limited as long as it is a compound that generates an acid by light. Specifically, a diarylsulfonium salt, a triarylsulfonium salt, a dialkylphenacylsulfonium salt, a diaryliodonium salt, an aryldiazonium Salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, nitrobenzyl esters, aromatic N-oxyimide sulfonates, aromatic sulfamides, benzoquinone diazide sulfonic acid esters, naphthoquinone diazide sulfonic acid esters, and the like are used. Two or more kinds of such compounds can be used in combination as needed, or can be used in combination with other sensitizers.

  Of these, diazonaphthoquinone photosensitizers such as naphthoquinonediazide sulfonate are preferred, and the following compounds having a 1,2-naphthoquinonediazide structure are particularly recommended.

［式中、Ｑは水素原子又は以下に示す化合物であり、同時に水素原子となることはない。］

[In formula, Q is a hydrogen atom or the compound shown below, and does not become a hydrogen atom simultaneously. ]

  The blending amount of the photosensitizer is usually preferably 1 to 100 parts by weight and 5 to 50 parts by weight with respect to 100 parts by weight of the poly (amic acid-imide) resin in order to improve the sensitivity and resolution during exposure. 10 to 30 parts by weight is more preferable. When the blending amount is less than 1 part by weight, the sensitivity at the time of exposure becomes insufficient, and it is necessary to increase the irradiation amount. On the other hand, when it exceeds 100 parts by weight, not only the sensitivity is greatly lowered, but also the mechanical strength of the film is remarkably lowered. Furthermore, problems such as film loss after imidation occur, which is not preferable.

(Positive pattern manufacturing method)
As a method for producing a pattern using the photosensitive resin composition of the present invention, for example, a photosensitive resin composition is applied on a support substrate, dried, exposed, developed, and heat treated to be positive type. Forming a polyimide film pattern.

  A case where the present invention is applied to a semiconductor device will be described as an example. First, this positive photosensitive resin composition was applied onto a substrate such as copper, silicon or glass using a spin coater or bar coater, and dried in warm air at 40 to 100 ° C. for 0.1 to 3 hours under light shielding, A photosensitive poly (amic acid-imide) resin film having a thickness of 1 to 5 μm is obtained. The film forming step is preferably performed at 100 ° C. or lower, preferably 80 ° C. or lower. Exceeding this temperature is not preferable because the diazonaphthoquinone photosensitizer tends to be thermally decomposed.

  In order to remove the residual solvent contained in the coating film, pre-baking may be performed at 80 to 100 ° C. for 1 to 30 minutes, but it is also effective to immerse the coating film in water for 1 to 5 minutes. Residual solvent may cause swelling of the film and pattern collapse during development, and it is preferable to remove the solvent sufficiently to obtain a clear pattern.

  Next, the i-line of a high-pressure mercury lamp is irradiated at room temperature for 10 seconds to 1 hour through a photomask on the coating film from which the residual solvent is removed. In addition to i-line, g-line, X-ray, electron beam, ultraviolet ray, visible light, etc. can be used, but those having a wavelength of 200 nm to 500 nm are preferable. Next, 0.05 to 10% by weight, preferably 0.1 to 5% by weight of an aqueous alkali solution is used for development for 10 seconds to 10 minutes at room temperature to dissolve and remove the irradiated portion, and further rinse with pure water. . Developers include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and di-n-propylamine. Secondary amines such as, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, and alkalis such as quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide An aqueous solution and an aqueous solution to which an appropriate amount of a water-soluble organic solvent or a surfactant is added can be preferably used.

  As a developing method, methods such as spraying, paddle, dipping, and ultrasonic waves are used. As a result, a desired positive pattern is formed on the substrate.

  Furthermore, this coating film is heat-treated at, for example, 150 to 430 ° C., preferably 200 to 400, particularly 250 to 350 ° C., so that the poly (amidic acid-imide) resin is imidized and has excellent film characteristics. A polyimide film is formed. The heat treatment can be performed in air, in a vacuum, or in an inert gas atmosphere, but is preferably performed in an inert gas atmosphere.

  The imidization reaction can also be performed chemically using a dehydrating cyclization reagent. That is, a polyimide film can also be obtained by immersing a poly (amidic acid-imide) resin film formed on a substrate in acetic anhydride containing a basic catalyst such as pyridine or triethylamine at room temperature for 1 minute to several hours. it can.

  The polyimide film thus obtained has excellent flexibility.

  Any of the photosensitive resin compositions of the present invention can be used in the same field as the conventional positive photosensitive resin compositions have been used. Specifically, it can be used for an electronic component as an insulating film such as a semiconductor device or a multilayer wiring board.

  In the photosensitive resin composition, depending on the purpose of use and its use, conventionally known antioxidants, end-capping agents, fillers, silane coupling agents, photopolymerization initiators, sensitizers, etc. You may mix | blend an additive in the grade which does not impair the effect of this invention.

(Other ingredients)
Additives may be added to the poly (amic acid-imide) resin of the present invention for the purpose of further improving physical properties. For example, polymer compounds such as polyester resin, polyimide resin, polyamideimide resin, polyamide resin, flame retardant, antifoaming agent, antioxidant and the like are exemplified.

As the antioxidant, a conventionally known antioxidant can be used without particular limitation. Examples of such antioxidants include phenol-based antioxidants, amine-based antioxidants, benzotriazole-based antioxidants, etc. Among them, phenol antioxidants are preferable, and in particular, the number of carbon atoms is 6 to 100, more preferably carbon number. A phenolic antioxidant of 10 to 80 is preferable in that it provides excellent heat resistance (retention rate of elastic modulus after long-term heating) to a poly (amide acid-imide) resin and a polyimide resin derived from the resin. . Specific examples of such phenolic compounds include 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, 4,4′-methylenebis (2,6-di-tert). -Butylphenol), 4,4-butylidenebis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl- 6-tert-butylphenol), 4,4′-isopropylidenebisphenol, 2,4-dimethyl-6-tert-butylphenol, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate] methane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert Butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,2′-dihydroxy-3,3-di (Α-methylcyclohexyl) -5,5′-dimethyldiphenylmethane, 2,2′-isobutylidenebis (4,6-dimethylphenol), 2,6-bis (2′-hydroxy-3′-tert-butyl) -5′-methylbenzyl) -4-methylphenol, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,5-di-tert-amylhydroquinone, 2,5-di-tert-butylhydroquinone, 1, 4-dihydroxyanthraquinone, 3-tert-butyl-4-hydroxyanisole, 2-tert-butyl-4-hydroxyanisole, 2 , 4-Dibenzoylresorcinol, 4-tert-butylcatechol, 2,6-di-tert-butyl-4-ethylphenol, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2′- Dihydroxy-4-methoxybenzophenone, 2,4,5-trihydroxybenzophenone, α-tocopherol, bis [2- (2-hydroxy-5-methyl-3-tert-butylbenzyl) -4-methyl-6-tert- Butylphenyl] terephthalate, triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert -Butyl 4-hydroxyphenyl) propionate] That. Among these, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4-butylidenebis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4, 4′-isopropylidenebisphenol, 2,4-dimethyl-6-tert-butylphenol, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,1,3 -Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3, -Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,6-di-tert-butylphenol, bis [2- (2-hydroxy-5-methyl) -3-tert-butylbenzyl) -4-methyl-6-tert-butylphenyl] terephthalate, triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1, 6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is preferred.

Such antioxidants can be used alone or in admixture of two or more. In the case of using an antioxidant, the amount added is 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the poly (amic acid-imide) resin. .

In the poly (amide acid-imide) resin of the present invention, a carboxyl group may be modified as necessary to introduce a photosensitive group via a salt-type complex, an amide bond, or an ester bond. it can.

Photosensitive groups are 2- (dimethylamino) ethyl methacrylate, 2- (diethylamino) ethyl methacrylate, 2- (dimethylamino) ethyl acrylate, diethylaminoethyl acrylate, isocyanatoethyl methacrylate, 1-isocyanatocarbonylstyrene, glycidyl acrylate, It is preferably derived from a monomer having a polymerizable double bond such as glycidyl methacrylate and allyl glycidyl ether.

  The poly (amide acid-imide) resin of the present invention is excellent in transparency, and when the poly (amide acid-imide) resin is made into a polyimide resin, it has excellent flexibility. Can be used for

Thus, according to the present invention, it is possible to obtain a poly (amidic acid-imide) resin that is excellent in transparency, can be chemically modified, and does not substantially generate siloxane-based outgas. The polyimide resin derived from the (amide acid-imide) resin has excellent flexibility. Further, a photosensitive resin composition capable of forming a cured product that can be alkali-developed using the poly (amic acid-imide) resin, has a cured product (film or film) that is excellent in flexibility and has a fine pattern forming ability. In particular, it can be used for various electronic devices such as a protective film of a semiconductor element, a liquid crystal alignment film, and an interlayer insulating film of an integrated circuit.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, the symbol of the compound in an Example and a comparative example, and the measurement of each characteristic are as follows.

(1) Abbreviation of compound [component (A)]
TDA: 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride (“Ricacid TDA-100” manufactured by Shin Nippon Chemical Co., Ltd.) )
[Component (B)]
BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane) (“BAPP” manufactured by Wakayama Seika Kogyo Co., Ltd.)
APB: 1,3-bis (3-aminophenoxy) benzene (“APB-N” manufactured by Mitsui Chemicals)
[Component (C)]
XTJ542: In the above general formula (3), R ³ is a methyl group, X, Z is a propylene group, Y is a tetramethylene group, and a + c = 5.0, b = 9.0 diamine (manufactured by Huntsman “Jeffamine XTJ -542 ") Total amine number (mg KOH / g) 109.8
XTJ504: In the general formula (3), ^{R 3} is a hydrogen atom, X an ethylene group, and a = 2, b = c = 0 diamine (Huntsman Corp. "JEFFAMINE XTJ504")
XTJ501: a diamine having a general formula (3) in which R ³ is a methyl group, X, Z are propylene groups, Y is an ethylene group, and a + c = 6.0, b = 12.5 (“Jeffamine XTJ-” manufactured by Huntsman) 501 ") Total amine number (mg KOH / g) 118.47
D2000: In the above general formula (3), R ³ is a methyl group, X is a propylene group and a = 33, b = c = 0 diamine (“Jeffamine D-2000” manufactured by Huntsman) Total amine value (mgKOH / g) 56.37
The total amine value was determined by the “standard oil analysis test method” established by the Japan Oil Chemical Association.
[(D) component]
TMEG: 1,2-ethylenebis (anhydrotrimellitate) (“Rikacid TMEG-100” manufactured by Shin Nippon Chemical Co., Ltd.)
ODPA: 4,4′-oxydiphthalic anhydride (“ODPA” manufactured by Manac)
[Reaction solvent]
GBL: γ-butyrolactone

(2) Resin concentration of poly (amic acid-imide) resin in GBL solution (varnish) The concentration (% by weight) of poly (amic acid-imide) resin was determined according to the following method.
Precisely weigh 10 mg of GBL solution (varnish) of poly (amidic acid-imide) resin (to the second decimal place) and set it in TG-DTA device (device name: EXSTAR6000, TG-DTA6200 manufactured by Seiko Instruments Inc.) The weight at 250 ° C. was measured under the following measurement conditions. It calculated according to the following formula (1) using the obtained measured value.
Measurement condition;
Temperature increase rate: 5 ° C / min Flowing nitrogen amount: 100ml / min Measurement start temperature: 30 ° C
(a formula)
Resin concentration in GBL solution (varnish) of poly (amic acid-imide) resin = (W1 / W0) × 100 (1)
W1: Weight of measurement sample at 250 ° C. (g)
W0: Weight of measurement sample before starting measurement (g)

(3) Acid value Based on JISK0070 (1992), about 1 g of a GBL solution of poly (amic acid-imide) resin was precisely weighed. GBL / ethanol neutralized with 0.1N potassium hydroxide ethanol solution prepared in advance and diluted with 30 ml of 1/1 (wt%), phenolphthalein as an indicator, 0.1N potassium hydroxide ethanol solution The acid value was measured by titration, and the acid value was converted to the pure poly (amide acid-imide) resin by using the resin concentration in the GBL solution (varnish) of the poly (amide acid-imide) resin used.

(4) Molecular Weight About 1 g of a GBL solution (varnish) of poly (amic acid-imide) resin was diluted with about 30 ml of dimethylformamide to prepare a sample solution for molecular weight measurement. About this sample solution, the number average molecular weight (Mn) and weight average molecular weight (Mw) of polyethylene oxide conversion were calculated | required on condition of the following using gel permeation chromatography (GPC).
Equipment: Shimadzu RID-6A
Column: ShodexGPC AD802-S, AD803-S, AD-804S and AD805S
Column temperature: 40 ° C
Eluent: (10 mmol / L-lithium bromide + 10 mmol / L-phosphoric acid) / dimethylformamide Flow rate: 1.0 mL / min
Detector: RI

(5) Light transmittance A molded body (20 μm) obtained by casting a GBL solution of a poly (amidic acid-imide) resin on a PET substrate, drying it at 100 ° C. for 30 minutes under normal pressure, and peeling it off the substrate is an ultraviolet-visible spectrophotometer. The light transmittance (%) at 365 nm was measured using UV-2550 (manufactured by Shimadzu Corporation).
Higher light transmittance means better transparency.

(6) Glass transition temperature (Tg) (° C)
A GBL solution of poly (amidic acid-imide) resin was cast on a glass substrate and subjected to thermal imidization reaction at 100 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour under normal pressure to obtain a polyimide resin. . The glass transition temperature (° C.) of the polyimide resin is expressed as a ratio (E ″ / E ′) of storage elastic modulus E ′ and loss elastic modulus E ″ under the following conditions using a dynamic viscoelasticity measuring device. The loss tangent tan δ was measured, and the maximum value of the obtained tan δ was defined as the glass transition temperature (Tg) (° C.).
Apparatus: RHEOGEL-E4000 manufactured by UPM
Measurement conditions: Tensile mode Waveform: Sine wave Frequency: 10Hz
Temperature rising rate: 5 ° C./min Note that the lower the glass transition temperature of the polyimide resin, the better the flexibility.

(7) Positive Photosensitive Evaluation 2,3,4-Tris (1-oxo-2-diazonaphthoquinone-5-sulfoxy) benzophenone as a diazonaphthoquinone photosensitizer in a GBL solution of a poly (amic acid-imide) resin Was added to 30 parts by weight with respect to 100 parts by weight of the poly (amic acid-imide) resin and dissolved. This was coated on a silicon wafer surface-treated with a silane coupling agent (“KBE-903” manufactured by Shin-Etsu Silicone Co., Ltd.), dried at 60 ° C. for 2 hours in a hot air dryer, and a photosensitive film having a film thickness of 4 to 5 μm. A characteristic film was obtained. This was prebaked at 100 ° C. for 10 minutes, and then irradiated with i-line of an epi-illumination type high pressure mercury lamp through an interference filter for 5 minutes through a photomask. The irradiation light intensity is 3 mW / cm ² . This was developed with a 1.0% by weight aqueous solution of sodium bicarbonate at 25 ° C. for 1 to 6 minutes, rinsed with water, and then dried at 60 ° C. for several minutes. Thermal imidization was carried out by raising the temperature stepwise in vacuum at 150 ° C. for 30 minutes and further at 250 ° C. for 1 hour.
In the positive photosensitivity evaluation, a pattern having a line width of 20 μm was visually confirmed.
A: A clear pattern was obtained. O: A pattern was obtained. Δ: A part of the pattern was unclear or a part of the pattern was missing. X: A pattern was not formed. A and B were practical levels.

[Example 1]
In a 500 ml four-necked flask equipped with a nitrogen inlet tube, a stirrer, a distillation outlet, and a thermometer, GBL 160 g, ethylcyclohexane 50 g, (A) component, TDA 48.3 g (0.161 mol), (B) component As BAPP 32.4 g (0.079 mol), and as component C), XTJ542 81.7 g (0.079 mol) was charged and heated to 180 ° C. while stirring under a nitrogen stream. The imidation reaction was carried out for 1 hour while distilling the produced water out of the system. After distilling off 2.8 g of produced water, which is half of the theoretically produced water, the reaction was stopped, GBL was added, and the resin concentration was adjusted to 35. The GBL solution of the poly (amidic acid-imide) resin of the present invention was obtained by adjusting to 5%. Table 1 shows the resin concentration in the GBL solution, the acid value of the obtained poly (amide acid-imide) resin, the number average molecular weight, the weight average molecular weight, the polydispersity, the light transmittance, and the poly (amide acid-imide) resin. Table 1 shows the glass transition temperature and the positive-type photosensitivity evaluation results in the case of using a polyimide resin.

Using this GBL solution of poly (amidic acid-imide) resin, it was dried at 100 ° C. under normal pressure for 30 minutes, and infrared absorption spectrum analysis was performed. As a result, characteristic absorption of the carbonyl group derived from the imide ring was confirmed at 1715 cm ⁻¹ and 1780 cm ⁻¹ , and specific absorption of amide groups 1640 cm ⁻¹ and 1540 cm ⁻¹ derived from amic acid was confirmed.

[Example 2]
In a 500 ml four-necked flask equipped with a nitrogen inlet tube, a stirrer, a distillation outlet, and a thermometer, GBL 160 g, ethylcyclohexane 50 g, (A) component, TDA 48.3 g (0.161 mol), (B) component Were charged with 32.4 g (0.079 mol) of BAPP and heated to 180 ° C. while stirring under a nitrogen stream. The imidation reaction was carried out for 4 hours while distilling the produced water out of the system, and the reaction was further completed at 180 ° C. for 1 hour while distilling off ethylcyclohexane. (Step (I)). Next, this reaction solution was cooled to 30 ° C., 81.7 g (0.079 mol) of XTJ542 was added as component (C), 80 g of GBL was added and reacted for 5 hours, GBL was added, and the resin concentration was 35. The GBL solution of the poly (amidic acid-imide) resin of the present invention was obtained by adjusting to 5% (step (II)). Table 1 shows the resin concentration in the GBL solution, the acid value of the obtained poly (amide acid-imide) resin, the number average molecular weight, the weight average molecular weight, the polydispersity, the light transmittance, and the poly (amide acid-imide) resin. Table 1 shows the glass transition temperature and the positive-type photosensitivity evaluation results in the case of using a polyimide resin.

Using this GBL solution of poly (amidic acid-imide) resin, it was dried at 100 ° C. under normal pressure for 30 minutes, and infrared absorption spectrum analysis was performed. As a result, characteristic absorption of the carbonyl group derived from the imide ring was confirmed at 1715 cm ⁻¹ and 1780 cm ⁻¹ , and specific absorption of amide groups 1640 cm ⁻¹ and 1540 cm ⁻¹ derived from amic acid was confirmed.

[Examples 3 to 10]
The same procedure as in Example 2 was carried out except that the components (B) and (C) used were changed to the charged moles shown in Table 1 to obtain a GBL solution of the poly (amic acid-imide) resin of the present invention. Table 1 shows the resin concentration in the GBL solution, the acid value of the obtained poly (amide acid-imide) resin, the number average molecular weight, the weight average molecular weight, the polydispersity, the light transmittance, and the poly (amide acid-imide) resin. Table 1 shows the glass transition temperature and the positive-type photosensitivity evaluation results in the case of using a polyimide resin.

[Comparative Example 1]
A GBL solution of poly (amidic acid-imide) resin was obtained in the same manner as in Example 2 except that TMEG was used at the charged moles shown in Table 2 instead of TDA. Table 2 shows the resin concentration in the GBL solution, the acid value of the obtained poly (amide acid-imide) resin, the number average molecular weight, the weight average molecular weight, the polydispersity, the light transmittance, and the poly (amide acid-imide) resin. Table 2 shows the glass transition temperature and the positive-type photosensitivity evaluation results when using a polyimide resin.

Using this GBL solution of poly (amidic acid-imide) resin, it was dried at 100 ° C. under normal pressure for 30 minutes, and infrared absorption spectrum analysis was performed. As a result, characteristic absorption of the carbonyl group derived from the imide ring was confirmed at 1715 cm ⁻¹ and 1780 cm ⁻¹ , and specific absorption of amide groups 1640 cm ⁻¹ and 1540 cm ⁻¹ derived from amic acid was confirmed.

[Comparative Example 2]
A GBL solution of poly (amidic acid-imide) resin was obtained in the same manner as in Example 7 except that ODPA was used in the charge moles shown in Table 2 instead of TDA. Table 2 shows the resin concentration in the GBL solution, the acid value of the obtained poly (amide acid-imide) resin, the number average molecular weight, the weight average molecular weight, the polydispersity, the light transmittance, and the poly (amide acid-imide) resin. Table 2 shows the glass transition temperature and the positive-type photosensitivity evaluation results when using a polyimide resin.

From Table 1, since the light transmittance at 365 nm of the poly (amic acid-imide) resin of this example is 65% or more, it is clear that the transparency is excellent.

  Further, the polyimide resin derived from the poly (amic acid-imide) resin of this example has a glass transition temperature of 35 ° C. or more, which is a heat resistance index, and a glass transition temperature, which is a flexibility index, of 120 ° C. Since it is the following, it is clear that it is excellent in heat resistance and a softness | flexibility.

  Furthermore, as a result of positive-type photosensitivity evaluation, it can be seen that a practical level pattern can be obtained.

  On the other hand, in Comparative Example 1, the light transmittance of the poly (amide acid-imide) resin using TMEG instead of TDA which is the tetracarboxylic dianhydride of Example 1 is 11% and does not show good transparency. . In addition, the polyimide resin derived from the poly (amic acid-imide) resin has a glass transition temperature of 25 ° C. or less, which is an index of heat resistance, is inferior in heat resistance, and, as a result of positive photosensitive evaluation, Does not form a pattern.

In Comparative Example 2, it can be seen that the poly (amidic acid-imide) resin using ODPA as the tetracarboxylic dianhydride does not show good transparency at 8%. Moreover, a pattern is not formed as a result of positive photosensitive evaluation.

According to the present invention, a poly (amide acid-imide) resin that is excellent in transparency, can be chemically modified, and does not substantially generate siloxane-based outgas is obtained. Since the induced polyimide resin has excellent flexibility, it can be used for various electronic devices such as a protective film for a semiconductor element, a liquid crystal alignment film, and an interlayer insulating film for an integrated circuit.

Claims (8)

In the presence of a reaction solvent, the tetracarboxylic dianhydride (A) represented by the following general formula (1), the aromatic diamine (B) represented by the following general formula (2), and the following general formula (3) A polyoxyalkylenediamine (C)
(A) Poly (amide acid-imide) resin obtained by copolymerizing the component 100 at a charged molar ratio in which the sum of the component (B) and the component (C) is in the range of 80 to 125.
General formula (1)

[Wherein, R ¹ and R ² are the same or different and each represents a hydrogen atom or a methyl group. ]
General formula (2)

[Wherein, M represents a divalent group selected from —O—, —SO ₂ —, —C (CH ₃ ) ₂ —, and —C (CF ₃ ) ₂ —, which may be the same or different. Also good. n represents an integer of 1 to 5. ]
General formula (3)

[Wherein R ³ represents a hydrogen atom or a methyl group. X and Z each represent an ethylene group or a propylene group. Y represents a linear or branched alkylene group having 2 to 4 carbon atoms. a, b and c are the same or different and each represents an integer of 0 to 50, and the sum of a + b + c is an integer of 2 to 50. ] A poly (amide acid-imide) resin obtained by copolymerizing a tetracarboxylic dianhydride (A), an aromatic diamine (B) and a polyoxyalkylene diamine (C),
The total charged molar ratio is in the range of 80 to 125 with respect to the component (A) 100, and the sum of the component (B) and the component (C), and
In the step (I) and the step (I) in which an imidization copolymerization reaction is performed in the presence of a reaction solvent at a charged molar ratio in the range of (A) component 100, (B) components 15 to 90, and (C) components 0 to 25. A step of subjecting the obtained reaction solution to an amidation copolymerization reaction at a charged molar ratio in the range of (B) component 0 to 25 and (C) component 10 to 85 with respect to (A) component in step (I) ( II),
A poly (amidic acid-imide) resin according to claim 1 comprising:   The poly (amic acid-imide) resin according to claim 1 or 2, wherein the molar ratio of the component (B) to the component (C) is in the range of (B) :( C) = 15: 85 to 90:10. .   The number average molecular weight is 3,000 to 100,000, the weight average molecular weight is 6,000 to 200,000, and the acid value is 5 to 250 mgKOH / g. Poly (amide acid-imide) resin.   A poly (amic acid-imide) varnish containing the poly (amic acid-imide) resin according to any one of claims 1 to 4 and an organic solvent.   A photosensitive resin containing the poly (amide acid-imide) resin according to any one of claims 1 to 4 and a photosensitive agent, or containing the poly (amide acid-imide) varnish and the photosensitive agent according to claim 5. Composition. In the presence of a reaction solvent, the tetracarboxylic dianhydride (A) represented by the following general formula (1), the aromatic diamine (B) represented by the following general formula (2), and the following general formula (3) A poly (alkylamido-imide) resin obtained by copolymerization reaction with polyoxyalkylenediamine (C),
The total charge molar ratio is in the range of 80 to 125 with respect to the component (A) 100 and the sum of the component (B) and the component (C), and
The reaction solution obtained in the step (I) in which the imidization polymerization reaction is performed at a charged molar ratio in the range of (A) component 100, (B) components 15 to 90, and (C) components 0 to 25, and the reaction solution obtained in step (I) The step (II) of subjecting the component (A) in the step (I) to an amidation polymerization reaction at a charged molar ratio in the range of 10 to 85 with respect to the components (B) 0 to 25 and the component (C),
A process for producing a poly (amic acid-imide) resin comprising:
General formula (1)

[Wherein, R ¹ and R ² are the same or different and each represents a hydrogen atom or a methyl group. ]
General formula (2)

[Wherein, M represents a divalent group selected from —O—, —SO ₂ —, —C (CH ₃ ) ₂ —, and —C (CF ₃ ) ₂ —, which may be the same or different. Also good. n represents an integer of 1 to 5. ]
General formula (3)

[Wherein R ³ represents a hydrogen atom or a methyl group. X and Z each represent an ethylene group or a propylene group. Y represents a linear or branched alkylene group having 2 to 4 carbon atoms. a, b and c are the same or different and each represents an integer of 0 to 50, and the sum of a + b + c is an integer of 2 to 50. ]   A method of using the poly (amic acid-imide) resin according to claim 1 for photosensitive resin applications.