TW201430059A - Production method of polymer solution, resin composition, production method of hardened film and polymer solution - Google Patents

Abstract

This invention is a production method of a polymer solution including the following procedures (a) to (d). (a) a synthesis procedure, reacting an amine component and an acid component in a solvent including N-methyl-2-pyrrolidone (NMP) to obtain a polymer solution mixture including a polyimide precursor or a polybenzoxazole precursor; (b) a separating procedure, adding water or a water solution and a solvent with a low boiling point to the polymer solution mixture, and removing a water layer by a separating operation to obtain a layer of the solvent with a low boiling point; (c) a procedure of adding a substituting solvent and a polar solvent to the layer of the solvent with a low boiling point; (d) a condensing procedure, after the procedure (c), removing the solvent with a low boiling point by distillation under reduced pressure.

Description

Method for producing polymer solution and polymer solution

The present invention relates to a method of producing a polymer solution and a polymer solution. More specifically, the present invention relates to a polymer solution which is a material of a heat resistant resin composition used in an electronic component or a display element and a photosensitive resin composition having heat resistance.

The surface protective film and the interlayer insulating film of the semiconductor element are polyimine resins which have excellent heat resistance, electrical properties, mechanical properties and the like. In recent years, in the process of increasing the integration and size of semiconductor devices, the thickness of the sealing resin package is reduced or miniaturized, and the surface mounting by reflow soldering is transferred. Further, a polyimide resin which is superior in mechanical properties and heat resistance as before is required. Further, polybenzoxazole is attracting attention from the viewpoint of expecting low dielectric constant.

Further, polylysine which is a precursor of a polyimide resin can be usually obtained by reacting a tetracarboxylic dianhydride as a raw material with a diamine in an organic solvent.

Alternatively, polyphthalate can be used as a precursor to the polyimide resin. The synthesis method of polyphthalate is roughly classified into the following three methods.

The first synthesis method is a method of reacting a diester dicarboxylic acid dichloride with a diamine (see Patent Document 1 and Patent Document 2). Since the reactivity of the diester dicarboxylic acid dichloride with the diamine is higher than the reactivity of the tetracarboxylic dianhydride with the diamine, in the present synthesis method, the high molecular weight polyg can be obtained in a shorter time than the polyamic acid. Proline. However, since the diester dicarboxylic acid dichloride has high reactivity, it is easily converted into a diester dicarboxylic acid by hydrolysis. Therefore, when water is mixed into the polymerization system, the molecular weight of the obtained polyphthalate is lowered, and the reproducibility of molecular weight is insufficient. In addition, there is a problem that chloride ions remain in the polymer.

The second synthesis method is a method of converting a carboxyl group of polyproline into an ester. After the polyamic acid is synthesized from tetracarboxylic dianhydride and a diamine, a desired esterifying agent is added and reacted to obtain a polyamidite ester (see Patent Document 3).

However, in this method, there is no simple reaction tracking method for esterification, and there is a problem that it is difficult to quantitatively esterify all the carboxyl groups.

The third synthesis method is a method of polycondensing a diester dicarboxylic acid with a diamine using a condensing agent. As the condensing agent, a carbonyl diimidazole or a phosphorus-based condensing agent or the like is known. In this method, a high molecular weight polyglycolate is obtained with good reproducibility. However, there is a problem that impurities derived from a condensing agent must be removed, and it is difficult to obtain a high-purity polyphthalate.

On the other hand, the most common method for the production of alkali-soluble poly-o-hydroxy amides as polybenzoxazole precursors is to make dicarboxylic acid dichlorides and appropriate A method of bis-o-aminophenol reaction.

In order to supplement the hydrogen chloride produced in the above reaction, a soluble base such as pyridine is usually added.

Further, in the above method for synthesizing a polyimide precursor or a polybenzoxazole precursor, N-methyl-2 is used in any of the methods in terms of solubility and reactivity of the raw materials and products. Pyrrolidone (NMP) as a solvent. The polyimine precursor or polybenzoxazole precursor synthesized in NMP is in a state containing a chloride ion which is a by-product during synthesis or a residue derived from a condensing agent or an active ester moiety (polymer mixing) liquid).

The polyimide precursor or the polybenzoxazole precursor and the solvent are obtained from the polymer mixture described above, and substantially no impurities such as by-products and chloride ions during synthesis (for example, about 5% by mass or less) are contained. The method of polymer solution is as follows: adding water and/or alcohol to the polymer mixture, precipitating the polyimide precursor or the polybenzoxazole precursor, filtering, removing the impurities, and filtering The obtained polyimine precursor or polybenzoxazole precursor is dried and dissolved in another organic solvent different from the synthetic solvent (NMP). The polymer solution obtained by this method can be directly applied to a substrate and heat-hardened to form a cured film, and a resin composition in which other components are added to the polymer solution can be applied to the substrate and heat-hardened. And a cured film is formed.

On the other hand, from the viewpoint of safety, it is desirable to reduce NMP in a polymer solution or a resin composition. Specifically, for example, the content of NMP in the polymer solution or the resin composition is made 0.1% or less.

[Prior Art Literature]

[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. Hei 11-315140

Patent Document 2: Japanese Patent Laid-Open Publication No. 2000-273172

Patent Document 3: Japanese Patent Laid-Open No. Hei 10-60109

The present invention has been made in view of the above circumstances, and an object thereof is to provide a polymer solution capable of reducing the content of NMP and the content of by-products generated during the synthesis of a polybenzazole precursor or a polybenzoxazole precursor. method.

Further, an object of the present invention is to provide a method for producing a polymer solution in which the viscosity of the obtained polymer solution becomes small with time.

According to the invention, the following method for producing a polymer solution or the like can be provided.

A method for producing a polymer solution comprising the following steps (a) to (d): (a) a synthesis step of causing an amine component and an acid component to comprise N-methyl-2-pyrrolidone (NMP) Reacting in a solvent to obtain a polymer mixture containing a polyimide precursor or a polybenzoxazole precursor; (b) a liquid separation step of adding water or an aqueous solution and a low boiling point solvent to the polymer mixture a step of removing a water layer by a liquid separation operation to obtain a low boiling point solvent layer; (c) a step of adding a replacement solvent and a polar solvent to the low boiling point solvent layer; (d) a concentration step, after the above step (c), The above low boiling point solvent was distilled off under reduced pressure.

2. The method for producing a polymer solution according to the above 1, wherein the polar solvent It is one or more solvents selected from the group consisting of dimethyl hydrazine, N-ethyl pyrrolidone, and dimethylformamide.

3. The method for producing a polymer solution according to the above 1 or 2, wherein the low boiling point solvent is selected from the group consisting of isobutanol, ethyl acetate, butyl acetate, diethyl ether, methyl tert-butyl ether, and methyl group. One or more solvents of ethyl ketone and methyl isobutyl ketone.

4. The method for producing a polymer solution according to any one of the above 1 to 3, wherein the replacement solvent is selected from the group consisting of γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether. More than one solvent.

5. The method for producing a polymer solution according to any one of the above 1 to 4, wherein the polybenzazole precursor or the polybenzoxazole precursor has the following general formula (I) or formula (II) ) the structure represented,

(In the formula (I), X represents a tetravalent organic group, p represents an integer of 0 to 2, and W is a divalent to tetravalent organic group; and R ¹ and R ² each independently represent a hydrogen atom, and the carbon number is 1~ An aliphatic group of 6 or a group represented by the following formula (Ia); [Chemical 2]

(In the formula (Ia), R ³ is a hydrogen atom or a methyl group, and a represents an integer of 1 to 6)

(In the formula (II), U is a tetravalent organic group, and V is a divalent organic group).

A polymer solution obtained by the method for producing a polymer solution according to any one of the above 1 to 5.

7. The polymer solution according to the above 6, wherein the content of the polar solvent is from 1% by mass to 20% by mass based on the whole.

8. The polymer solution according to the above 6 or 7, wherein the content of the nonvolatile matter is from 10% by mass to 50% by mass based on the whole.

A resin composition comprising the polymer solution according to any one of the above 6 to 8.

A method for producing a cured film, comprising: applying the polymer solution according to any one of the above 6 to 8 or the resin composition according to the above 9 to a substrate and drying to obtain a resin film And a step of heating the resin film.

According to the present invention, it is possible to provide a content which can reduce the content of NMP and the by-products produced by the synthesis of a polyimide precursor or a polybenzoxazole precursor. A method of producing a polymer solution.

Further, a production method in which the viscosity change of the obtained polymer solution becomes small with time can be provided.

1‧‧‧Semiconductor substrate

2‧‧‧Protective film

3‧‧‧1st conductor layer

4‧‧‧Interlayer insulating film

5‧‧‧Photosensitive resin layer

6A, 6B, 6C‧‧‧ windows

7‧‧‧2nd conductor layer

8‧‧‧Surface protective film

1 is a schematic cross-sectional view for explaining a manufacturing procedure of a semiconductor device having a multilayer wiring structure according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail. In addition, in the present specification, the term "step" is not only an independent step but also includes the term as long as the intended effect of the step can be achieved even if it cannot be clearly distinguished from other steps. in.

Further, the numerical range indicated by "~" indicates a range in which the numerical values described before and after the "~" are respectively included as the minimum value and the maximum value.

<Method for Producing Polymer Solution>

The method for producing a polymer solution of the present invention comprises the following steps (a) to (d).

(a) a synthesis step of reacting an amine component with an acid component in a solvent containing N-methyl-2-pyrrolidone (NMP) to obtain a polymerization containing a polyimide precursor or a polybenzoxazole precursor Mixture

(b) a liquid separation step of adding water or an aqueous solution and a low boiling point solvent to the above polymer mixture, and removing the water layer by a liquid separation operation to obtain a low boiling point solvent layer

(c) a step of adding a replacement solvent and a polar solvent to the low-boiling solvent layer

(d) a concentration step, after the above step (c), the above low boiling point solvent is distilled off under reduced pressure

In order to reduce the NMP content of the polymer solution, it is considered to replace the solvent used in the case of synthesizing the polyimine precursor or the polybenzoxazole precursor into a solvent other than NMP, such as γ-butyrolactone (BLO) ). However, there are problems in the case where the monomer of the raw material is not dissolved or the case where the synthesis reaction does not proceed. Further, even if a reaction accelerator is added, there is a problem that the accelerator does not dissolve and remains.

In addition, the following method is also considered: adding water and/or alcohol to the polymer mixture, precipitating the polyimide precursor or the polybenzoxazole precursor, filtering, drying and recovering, and recovering the recovered precursor The polymer is dissolved in another organic solvent different from the NMP solvent, such as BLO, to form a polymer solution. However, in this method, it is difficult to make NMP 1% or less.

The present inventors have found that by combining the above steps (a) to (d), it is possible to obtain a reduction in the content of NMP and the content of by-products produced during the synthesis of the polybenzazole precursor or the polybenzoxazole precursor. Polymer solution. Further, it was found that the change in the viscosity of the obtained polymer solution with time became small.

Hereinafter, each step will be described.

<(a) Synthesis step>

In the synthesis step, the amine component is reacted with an acid component using N-methyl-2-pyrrolidone (NMP) as a solvent to obtain a polymer mixture containing a polyimide precursor or a polybenzoxazole precursor. .

The polyimine precursor may be exemplified by polyamine or polyphthalate. The polybenzoxazole precursor may, for example, be poly-o-hydroxy decylamine.

(polyglycine)

Polylysine can be obtained, for example, by reacting a tetracarboxylic dianhydride as an acid component with a diamine compound as an amine component. For example, polylysine can be synthesized according to the method described below.

First, the diamine compound is dissolved in an organic solvent. To the solution, a molar amount of tetracarboxylic dianhydride substantially equivalent to a diamine compound was gradually added, and the reaction was carried out while stirring using a mechanical stirrer. When the terminal sealant is used, after the tetracarboxylic dianhydride is added, the terminal sealant may be added slowly after stirring at the temperature and the required time, and may be added in one shot to cause a reaction.

The diamine compound may, for example, be 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylanthracene, 4,4'-di Aminodiphenyl sulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)fluorene , bis(3-aminophenoxyphenyl)anthracene, bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, 1,4- An aromatic diamine compound such as bis(4-aminophenoxy)benzene; LP-7100, X-22-161AS, X-22-161A, X-22-161B, X-22-161C and X-22- 161E (all manufactured by Shin-Etsu Chemical Co., Ltd., trade name) and other ketone-containing diamine compounds; 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'- Amino-3,3'-dihydroxybiphenyl, Bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)anthracene, bis(4-amine 3-hydroxyphenyl)indole, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-dual ( A diamine compound having a hydroxyl group such as 4-amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane or the like.

Among these, a diamine compound having a hydroxyl group is preferred, and 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexa is more preferred. Fluoropropane. Further, the diamine compound is not limited to these. These compounds may be used alone or in combination of two or more.

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 2,3,3',4'-biphenyltetracarboxylic dianhydride. , 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-di Benzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1 - bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane Anhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2 , 3,4-cyclopentane tetracarboxylic dianhydride, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,2,5,6-naphthalenetetracarboxylic dianhydride , 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-decanetetracarboxylic dianhydride, 3,3' 4,4'-tetraphenylnonanetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and the like. These may be used alone or in combination of two or more. Further, the tetracarboxylic dianhydride is not limited to these.

Among the above tetracarboxylic dianhydrides, in view of obtaining good film physical properties with high heat resistance, pyromellitic dianhydride and 3,3',4,4'-biphenyltetracarboxylic acid are preferred. Anhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-di Benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 2,2-bis ( 3,4-dicarboxyphenyl)hexafluoropropane dianhydride, N-(trimellitic dianhydride)-2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, more preferably It is bis(3,4-dicarboxyphenyl)ether dianhydride.

In the synthesis of polylysine, the solvent is a mixture of NMP alone or NMP and an organic solvent.

Further, the organic solvent mixed with NMP may be N,N-dimethylacetamide, N,N-dimethylformamide, N-ethylidene-2-pyrrolidone or hexamethylphosphonium. Amine, dimethylimidazolidinone, N-ethinyl-ε-caprolactam and the like.

In the synthesis of poly-proline, the amine component and the acid component are preferably reacted in a molar ratio (amine component/acid component) of 0.5 to 1.5, more preferably in a molar ratio (amine component/acid component) of 0.75 to 1.25. reaction.

The reaction temperature is preferably from -20 ° C to 100 ° C, more preferably from 10 ° C to 50 ° C. The reaction time is preferably from 0.5 to 100 hours, more preferably from 2 to 24 hours.

(polyglycolate)

The polyperurethane can be obtained, for example, by reacting a tetracarboxylic acid diester dichloride as an acid component with a diamine as an amine component. For example, a polyphthalate can be synthesized by mixing a tetracarboxylic dianhydride with a hydroxyl group-containing compound and reacting it to produce a half ester of a tetracarboxylic acid, followed by a halogenating agent. A method of hydrazine chlorination, followed by reaction with a diamine, or a method of reacting the above tetracarboxylic acid half ester with a diamine using a carbodiimide as a condensing agent.

As the acid component of the polyphthalate, tetracarboxylic dianhydride can be used as described above The same tetracarboxylic dianhydride is synthesized from polylysine.

As the amine component of the polyperurate, the same diamine compound as that of the above polyamic acid can be used.

In the formation of the half ester of polyamic acid, an aliphatic alcohol such as methanol, ethanol, propanol or butanol can be used as the hydroxyl group-containing compound.

A halogenating agent for halogenating a half ester of polyamic acid can be a sulfonium chloride, a phosphoryl chloride, a phosphorous oxychloride or a fifth used in a hydrazine chlorination reaction of a usual carboxylic acid. Phosphorus chloride and the like.

The carbodiimide condensing agent which reacts the half ester of the polyamic acid with the diamine is not particularly limited as long as it is a carbodiimide condensing agent used in the usual active ester synthesis, and examples thereof include a bicyclic ring. Hexylcarbodiimide, diisopropylcarbodiimide, N-[3-(dimethylamino)propyl]-N-ethylcarbodiimide, 1-ethyl-3-(3- Dimethylaminopropyl) carbodiimide hydrochloride or the like.

In the synthesis of the polyglycolate, the solvent is a mixture of NMP alone or NMP and the above organic solvent. The solvent is preferably used in an amount of 100 parts by weight or more and 1500 parts by weight or less based on 100 parts by weight of the polymer obtained.

In the synthesis of the polyglycolate, the amine component and the acid component preferably react with a molar ratio (amine component/acid component) of 0.5 to 1.5, more preferably a molar ratio (amine component/acid component) of 0.75~ 1.25 reaction.

The reaction temperature for the synthesis of the polyglycolate is preferably from -10 ° C to 90 ° C, more preferably from 0 ° C to 70 ° C. The reaction time is preferably from 8 hours to 1 week, more preferably from 10 hours to 42 hours.

(polybenzoxazole precursor)

The polybenzoxazole precursor can be obtained, for example, by reacting a dicarboxylic acid dihalide as an acid component with a dihydroxydiamine compound as an amine component. For example, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting with the above diamine compound. The dihalide derivative is preferably a dichloride derivative.

Examples of the dicarboxylic acid include isophthalic acid, terephthalic acid, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 4,4'- Dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylnonane, bis(4-carboxyphenyl)anthracene, 2,2-bis(p-carboxyphenyl)propane , an aromatic dicarboxylic acid such as 5-t-butylisophthalic acid, 5-broloisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid or 2,6-naphthalenedicarboxylic acid Acid; 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, oxalic acid, malonic acid, succinic acid, dodecanedioic acid, etc. Aliphatic dicarboxylic acid and the like.

Among these, 4,4'-dicarboxydiphenyl ether or an aliphatic dicarboxylic acid is preferred, and 4,4'-dicarboxydiphenyl ether or dodecanedioic acid is more preferred.

In addition, it is not limited to these. These compounds may be used alone or in combination of two or more.

As the dihydroxydiamine compound, the above-mentioned synthetic diamine having a hydroxyl group which can be used for the synthesis of polyamic acid can be used.

The dihalide derivative can be synthesized by allowing a halogenating agent to act on a dicarboxylic acid derivative. As the halogenating agent, sulfinium chloride, phosphonium chloride, phosphorus oxychloride, phosphorus pentachloride or the like used in the hydrazine chlorination reaction of a usual carboxylic acid can be used.

As a method for synthesizing a dihalide derivative, a dicarboxylic acid derivative can be utilized. The product is reacted with the above halogenating agent in a solvent or after being reacted in an excess of a halogenating agent, and an excess portion is distilled off. As the reaction solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N,N-dimethylacetamide, N,N-dimethylformamide, toluene, benzene can be used. Wait.

The amount of the halogenating agent to be used is preferably from 1.5 mol to 3.0 mol, more preferably from 1.7 mol to 2.5 mol, based on the dicarboxylic acid derivative, in the case of carrying out the reaction in a solvent. In the case of carrying out the reaction in the halogenating agent, it is preferably from 4.0 mol to 50 mol, more preferably from 5.0 mol to 20 mol. The reaction temperature is preferably -10 ° C to 70 ° C, more preferably 0 ° C to 20 ° C.

The reaction of the dihalide derivative with the diamine compound is carried out in the presence of a dehydrohalogenating agent in NMP or in a mixed solvent of NMP and the above organic solvent. As the dehydrohalogenating agent, an organic base such as pyridine or triethylamine can be usually used.

The diamine compound and the dihalide derivative are preferably reacted in a molar ratio (amine component/dihalide derivative) of 0.5 to 1.5, more preferably in a molar ratio (amine component/dihalide derivative) of 0.75~ 1.25 reaction.

The reaction temperature is preferably -10 ° C to 30 ° C, more preferably 0 ° C to 20 ° C. The reaction time is preferably from 3 hours to 24 hours, more preferably from 6 hours to 12 hours.

Alternatively, the polybenzoxazole precursor can be synthesized by a method via a dicarboxylic acid active ester. Specifically, the dicarboxylic acid is reacted in the presence of dicyclohexylcarbodiimide and 1-hydroxy-benzotriazole. In this reaction, a polybenzoxazole precursor can be obtained by temporarily forming an active ester from an aromatic dicarboxylic acid and 1-hydroxy-benzotriazole, followed by reaction with a diamine having a hydroxyl group.

The dicarboxylic acid described in the synthesis of the above polybenzoxazole precursor can be used as the dicarboxylic acid used in the above reaction.

As the diamine compound, the above-mentioned synthetic diamine having a hydroxyl group which can be used for the synthesis of polyamic acid can be used.

The reaction of the dicarboxylic acid active ester with the diamine compound is carried out in NMP or in a mixed solvent of NMP and the above organic solvent.

The diamine compound and the dicarboxylic acid active ester are preferably reacted in a molar ratio (amine component/acid active ester) of 0.5 to 1.5, more preferably in a molar ratio (amine component/acid active ester) of 0.75 to 1.25.

The reaction temperature is preferably from 0 ° C to 90 ° C, more preferably from 20 ° C to 75 ° C. The reaction time is preferably from 3 hours to 3 days, more preferably from 6 hours to 24 hours.

The both ends of each of the above polyimine precursors or polybenzoxazole precursors may be made into an acidic functional group or a derivative thereof. The method for causing the both ends to be an acidic functional group or a derivative thereof may be carried out by reacting the diamine component and the acid component with a molar ratio (amine component/acid component) of 1 to 1.5, but more preferably The diamine component and the acid component are reacted in a molar ratio (amine component/acid component) of 1.05 to 1.25. In this case, both end portions of the obtained precursor are carboxyl groups.

The carboxyl group can in turn be substituted with other acidic functional groups or derivatives thereof.

A specific method of introducing a functional group into a carboxyl group at the terminal portion is a method of adding a monoamine compound having a functional group or a functional group at the time of synthesis of the precursor.

The above monoamine-based compound may, for example, be ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, tert-butylamine, diethylamine, dipropylamine or diisopropyl. Aliphatic amines such as alkamine, dibutylamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cyclohexylmethylamine; aniline, o-toluidine, m-toluidine, p-toluidine An aromatic amine such as o-aminophenol, m-aminophenol or p-aminophenol. Further, the monoamine-based compound is not necessarily limited to these.

Among them, from the viewpoint of stability, it is preferred to add a monoamine compound having an acidic functional group such as an o-aminophenol, a m-aminophenol or a p-aminophenol, and the like, and the terminal is an acidic functional group. Or its derivatives.

In the present invention, the polyiminamide precursor or the polybenzoxazole precursor preferably has the following formula (I) or formula (II) from the viewpoint of solubility in the developer. The compound of the structure indicated.

(In the formula (I), X represents a tetravalent organic group, p represents an integer of 0 to 2, and W is a divalent to tetravalent organic group. R ¹ and R ² each independently represent a hydrogen atom or have a carbon number of 1 An aliphatic group of ~6 or a group represented by the following formula (Ia)).

(In the formula (Ia), R ³ is a hydrogen atom or a methyl group, and a represents an integer of 1 to 6)

(In the formula (II), U is a tetravalent organic group and V is a divalent organic group)

In the general formula (I), the tetravalent organic group as X is a residue of tetracarboxylic dianhydride as a raw material. Specifically, a tetravalent aromatic group or a tetravalent aliphatic group is preferred. The carbon number is preferably from 4 to 40. More preferably, it is a tetravalent aromatic group having a carbon number of 4 to 40 or a tetravalent aliphatic group having a carbon number of 4 to 40.

p represents an integer from 0 to 2, indicating that 0 to 2 hydroxyl groups are bonded to W.

The divalent to tetravalent organic group of W is a residue of a diamine as a raw material, preferably a divalent to tetravalent aromatic group or a divalent to tetravalent aromatic aliphatic group, more preferably A divalent to tetravalent aromatic group having a carbon number of 4 to 40.

R ¹ and R ^{2 are} preferably hydrogen, an alkyl group having 1 to 6 carbon atoms or a group represented by the above formula (Ia).

The content of the structural unit represented by the formula (I) in the precursor is preferably from 60 mol% to 100 mol%, more preferably from 80 mol% to 100 mol%.

In the formula (II), the tetravalent organic group represented by U is a residue of a diamine having a structure in which two hydroxyl groups are ortho to the amine, respectively. U is preferably The tetravalent aromatic group, in addition, preferably has a carbon number of 6 to 40. More preferably, it is a tetravalent aromatic group having 6 to 40 carbon atoms. The tetravalent aromatic group is preferably a tetravalent aromatic group in which four bonding sites are present on the aromatic ring.

The divalent organic group represented by V is a residue of the dicarboxylic acid as a raw material, preferably a divalent aromatic group or a divalent aliphatic group, and the carbon number is preferably 6 to 40. More preferably, it is a divalent aromatic group or a divalent aliphatic group having 6 to 40 carbon atoms.

The content of the structural unit represented by the formula (II) in the precursor is preferably from 60 mol% to 100 mol%, particularly preferably from 80 mol% to 100 mol%.

The polybenzoxazole precursor preferably has a structure represented by the formula (II), and the solubility of the polybenzoxazole precursor to the aqueous alkali solution is preferably a certain ratio or more because it is derived from a phenolic hydroxyl group. A hydroxy unit containing an amide unit. That is, a polybenzoxazole precursor represented by the following formula (III) is preferred.

(wherein U represents a tetravalent organic group, and V and Y respectively represent a divalent organic group. j and k represent a molar fraction, the sum of j and k is 100 mol%, and j is 60 mol% to 100 mol. Ear %, k is 40 mole % ~ 0 mole %)

In the formula (III), U and V are the same as the above formula (II).

The divalent organic group represented by Y is a residue of a diamine as a raw material, and is formed. Residues other than the diamine of U. Y is preferably a divalent aromatic group or a divalent aliphatic group, and preferably has a carbon number of 4 to 40, more preferably a divalent aromatic group having 4 to 40 carbon atoms. Further, it is preferable that j is from 80 mol% to 100 mol%, and k is from 20 mol% to 0 mol%.

The weight average molecular weight (Mw) of the polyimine precursor or the polybenzoxazole precursor in the present invention is 5,000 to 100,000 in terms of polystyrene. It is preferably 7,000 to 80,000, more preferably 10,000 to 60,000. In terms of improving heat resistance, it is preferably 5,000 or more. On the other hand, it is preferably 100,000 or less in terms of solubility in a solvent or workability.

The polymer mixture of the polyimine precursor or the polybenzoxazole precursor obtained by the present step comprises a polyiminamide precursor or a polybenzoxazole precursor, NMP, and a by-product in the synthesis step ( Hydrochloride, etc.), and impurities. In this stage, a large amount (for example, 50% by mass or more) of NMP is contained in the polymer mixture.

Further, for example, the hydrochloride as a by-product is produced by a base such as pyridine which is produced by a reaction between a dicarboxylic acid dichloride and a diamine and a pyridine which is added as a trapping agent for hydrochloric acid.

<(b) Liquid separation step>

In this step, water or an aqueous solution and a low boiling point solvent are added to the polymer mixture obtained in the above step (a), and the aqueous layer is removed by a liquid separation operation to obtain a low boiling point solvent layer. By this step, impurities such as a hydrochloride which is a by-product of the synthesis of the polyimide precursor or the polybenzoxazole precursor can be removed from the NMP as a solvent.

The liquid separation step can be carried out, for example, by the following method.

First, a low boiling point solvent is appropriately added to the polymer mixed liquid so that the content of the solid component (polyimine imide precursor or polybenzoxazole precursor) is 3% by mass to 30% by mass.

The low boiling point solvent is as long as it can be separated from the solvent containing NMP and the water or aqueous solution added in this step, and the polybenzazole precursor or the polybenzoxazole precursor is dissolved, which is lower than that used in the subsequent step. The organic solvent of the solvent and the boiling point of the polar solvent is not particularly limited. The boiling point of the low boiling point solvent is not particularly limited, but is preferably 180 ° C or lower.

Examples of the low boiling point solvent include isobutyl alcohol, ethyl acetate, butyl acetate, diethyl ether, methyl tertiary butyl ether, methyl ethyl ketone, methyl isobutyl ketone, hexane, and benzene. Further, organic solvents other than the above may be used, and they may be used singly or in combination.

Among these, from the viewpoints of solubility of the volatile, polyimine precursor or polybenzoxazole precursor, and layer separation from the aqueous layer, ethyl acetate and methyl group are preferred. Butyl ketone or methyl tert-butyl ether.

Next, water or an aqueous solution is added to the polymer mixture to which the low boiling point solvent is added.

The aqueous solution may, for example, be an aqueous solution of an inorganic acid, an organic acid or an inorganic salt, and specific examples thereof include ion-exchanged water, aqueous hydrochloric acid solution, aqueous sulfuric acid solution, aqueous nitric acid solution, aqueous acetic acid solution, aqueous oxalic acid solution, and aqueous sodium chloride solution. Further, an aqueous solution other than the above may also be used. Among them, ion-exchanged water is preferred.

Water or aqueous solution as a whole with respect to the polymer mixture to which the low boiling point solvent is added The amount of addition is preferably from 10% by mass to 200% by mass.

Stirring is carried out after adding water or an aqueous solution. The stirring time is preferably from 5 minutes to 60 minutes, more preferably from 10 minutes to 20 minutes.

After stirring, if left to stand, it is separated into two layers of a low boiling point solvent layer (upper layer) and a water layer (lower layer). In the two layers obtained by the separation, the water layer was removed by a liquid separation operation.

The low boiling point solvent layer contains a polyimide intermediate or a polybenzoxazole precursor and a low boiling point solvent. The aqueous layer contains impurities such as chloride ions, NMP, and water which are produced by a water-soluble compound such as a polyimide precursor or a polybenzoxazole precursor.

The standing time after the stirring is the time until the completion of the separation, and is usually 10 minutes to 2 hours, but is not particularly limited. By this step, a low boiling point solvent layer containing a polyimide intermediate or a polybenzoxazole precursor and a low boiling point solvent can be obtained.

In addition, the dispensing step can be performed as many times as needed. By performing a plurality of times, NMP or the like can be further removed, and the content of NMP or impurities in the finally obtained polymer solution can be reduced.

Further, after liquid separation is carried out by adding water or an aqueous solution and a solvent having a low boiling point, a step of separately separating the liquid using only water or an aqueous solution may be carried out.

Further, in the above description, water or an aqueous solution is added after the addition of the low boiling point solvent, but a low boiling point solvent may be added after the addition of water or an aqueous solution.

<(c) Step of adding a replacement solvent and a polar solvent to a low-boiling solvent layer>

In this step, a replacement solvent and a polar solvent are added to the low boiling point solvent layer obtained by the above step (b). Further, the order of adding the replacement solvent and the polar solvent is not limited, and any solvent may be added first, or may be added at the same time.

The replacement solvent used in this step becomes a main component of the solvent of the finally obtained polymer solution. The substitution solvent is not particularly limited as long as it is an organic solvent which dissolves the polyimide precursor or the polybenzoxazole precursor and has a boiling point higher than the low boiling solvent used in the above step.

Specific examples thereof include γ-butyrolactone (GBL), ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, and 3-methylmethyl. Oxypropionate, N,N-dimethylformamide, N,N-dimethylacetamide, hexamethylphosphoniumamine, tetramethylenesulfonium, diethylketone, diisobutylene Ketone, methyl amyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether and the like. These solvents may be used singly or in combination of two or more.

Among these, from the viewpoint of solubility of the polyimide precursor or the polybenzoxazole precursor, it is preferred to use γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, Propylene glycol monomethyl ether.

In addition, the amount of the substitution solvent to be added is not particularly limited, and it is preferably adjusted so that the ratio of the replacement solvent in the finally obtained polymer solution is 20% by mass to 90% by mass.

The polar solvent used in this step has a function of preventing the change of the viscosity of the polymer solution over time. Previously, the main component of the solvent in the polymer solution was NMP, but if the content of NMP was reduced from the viewpoint of safety, the polymer was present. The problem of the viscosity of the solution changing over time. The polar solvent used in this step prevents hydrogen bonding between the molecules of the polyimidazole precursor or the polybenzoxazole precursor. As a result, it is considered that the temporal change of the viscosity of the polymer solution can be prevented.

Examples of the polar solvent include dimethyl hydrazine (DMSO), N-ethylpyrrolidone (NEP), or dimethylformamide (DMF). Among these, DMSO and NEP are preferably used in terms of preventing the change of viscosity over time.

The amount of the polar solvent to be formulated is not particularly limited. It is preferred to adjust so that the ratio of the polar solvent in the finally obtained polymer solution is 1% by mass to 20% by mass.

<(d) Concentration step>

In this step, a low boiling point solvent is distilled off from a low boiling point solvent layer obtained by adding a substitution solvent and a polar solvent to the above step (c), and concentrated under reduced pressure. In the concentration step, the low boiling point solvent and residual moisture are removed to obtain a polymer solution.

The method of the concentration step is not particularly limited. For example, the low-boiling solvent layer after the step (c) is depressurized by using a vacuum pump, and concentrated under reduced pressure at a temperature of 20 ° C to 100 ° C at a temperature of 30 ° C to 60 ° C for 12 hours to 1 week. Yes, it is better for 1 day to 3 days.

Further, after the concentration step, if necessary, the concentration of the volatile component may be adjusted by dilution with a low boiling point solvent and/or a replacement solvent.

By the above steps (a) to (d), a polymer solution in which the content of NMP is extremely small and the by-products generated when the polyimide precursor or the polybenzoxazole precursor is synthesized can be obtained. In addition, a small change in viscosity over time can be obtained. Compound solution.

<Polymer solution and resin composition>

The polymer solution of the present invention can be obtained, for example, by the above-described production method of the present invention.

Regarding the polymer solution of the present invention, for example, the content of NMP in the polymer solution is as small as 0.1% by mass or less, and impurities (for example, chloride) which are produced when the polyimide precursor or the polybenzoxazole precursor is synthesized. There are also few ions (for example, 0.1% by mass or less). Further, it is a polymer solution having a small change in viscosity of the obtained polymer solution with time.

In the polymer solution of the present invention, the concentration of the volatile component is preferably from 50% by mass to 90% by mass. When the volatile component is in this range, the resin solution or the resin composition in which another component is added to the polymer solution is applied to the substrate and heat-cured to form a cured film, and it is easy to form a moderate thickness ( A film of 0.1 μm to 50 μm). Further, the concentration of the volatile component in the polymer solution can be determined by quantifying a volatile component (the above-mentioned replacement solvent or polar solvent) by gas chromatography.

The resin composition of the present invention contains the polymer solution of the present invention. The resin composition of the present invention may be newly added with a solvent as needed, and may further contain a photosensitizer, an acid generator, a radical initiator, a adhesion aid, a crosslinking agent, and the like.

<Method for Producing Cured Film>

The method for producing a cured film of the present invention comprises the steps of: applying the above polymer solution or resin composition of the present invention onto a substrate and drying to obtain a resin film; And a step of heating the resin film. Further, the technical scope of the present invention also relates to a cured film obtained by the above production method.

In the step of obtaining a resin film, a polymer solution or a resin composition is spin-coated on a glass substrate, a semiconductor, a metal oxide insulator (TiO ₂ , SiO _{2 ,} etc.), nitrogen using a spinner or the like. After baking on a substrate such as ruthenium, it is dried using a hot plate, an oven, or the like to form a resin film.

Further, the resin film can be formed into a pattern resin film by a known exposure step, development step, or the like.

In the step of heating the resin film, the resin film is subjected to a heat treatment at 150 ° C to 450 ° C to obtain a cured film. A diffusion furnace, an oven, a hot plate, or the like can be used for the heat treatment.

The time until the resin film is thermally cured is a time period until the scattering of the residual solvent or the volatile component is sufficiently performed, and the work efficiency is approximately 5 hours or less. In addition, the heat treatment environment may be selected from any environment in the atmosphere or in an inert environment such as nitrogen.

The cured film obtained in the above manner can be used as a surface protective layer, an interlayer insulating layer, a rewiring layer, or the like in a semiconductor device.

An example of a manufacturing procedure of a semiconductor device (electronic component) using the polymer solution or the resin composition of the present invention will be described below. 1 is a manufacturing step diagram of a semiconductor device having a multilayer wiring structure.

In FIG. 1, a semiconductor substrate 1 such as a Si substrate having circuit elements is a circuit. The protective layer 2 such as a tantalum oxide film is covered by a specific portion of the element, and the first conductor layer 3 is formed on the exposed circuit element. The interlayer insulating film layer 4 such as a polyimide resin as an interlayer insulating film is formed on the semiconductor substrate by a spin coating method (step (a) in Fig. 1).

Next, a chlorinated rubber-based or phenol novolak-based photosensitive resin layer 5 is formed on the interlayer insulating film layer 4 by a spin coating method, and a specific portion of the interlayer is formed by a known photo etching technique. The window 6A is provided in such a manner that the insulating film layer 4 is exposed (step (b)). The interlayer insulating film 4 exposed by the above-described window 6A is selectively etched by a dry etching method using gas such as oxygen gas or carbon tetrafluoride to open the window 6B. Then, the photosensitive resin layer 5 is completely removed by using the etching solution which etches only the photosensitive resin layer 5 without etching the first conductor layer 3 exposed from the window 6B (step (c)).

Further, the second conductor layer 7 is formed by a known photo etching technique, and electrical connection with the first conductor layer 3 is completely performed (step (d)). In the case of forming a multilayer wiring structure of three or more layers, the above steps can be repeated to form each layer.

Next, the surface protective film layer 8 is formed. In this example, the surface protective film layer is coated with a polymer solution or a resin composition of the present invention by a spin coating method and dried, and a mask on which a pattern of the window 6C is formed is drawn from a specific portion. After the light is irradiated, development is carried out by an aqueous alkali solution to form a pattern, and heating is performed to obtain a heat-resistant polymer film. The heat-resistant polymer film protects the conductor layer from external stresses, α rays, and the like, and is excellent in reliability of the obtained semiconductor device. Further, in the above examples, the polymer solution or resin composition of the present invention may also be used. Interlayer insulating film layer.

[Examples]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples. Further, as long as there is no special description, the reagents are all used in the chemicals. In addition, "%" means "% by mass" unless otherwise specified. Further, the physical properties and the like of the compounds in the examples and the comparative examples were measured by the following methods.

<Method for Measuring Weight Average Molecular Weight (Mw)>

The weight average molecular weight of the polyimide precursor and the polybenzoxazole precursor is Gel Permeation Chromatography (GPC, the device is manufactured by Hitachi, Ltd., and the column is limited by Hitachi Chemical Co., Ltd. Gelpack manufactured by the company is obtained by standard polystyrene conversion. Specifically, the weight average molecular weight of each polymer was measured by GPC under the following apparatus and conditions.

Measuring device: detector L4000UV manufactured by Hitachi, Ltd.

Pump: L6000 manufactured by Hitachi, Ltd.

C-R4A Chromatopac manufactured by Shimadzu Corporation

Measurement conditions: column Gelpack GL-S300MDT-5×2

Dissolution: Tetrahydrofuran (THF) / DMF = 1 / 1 (volume ratio)

LiBr (0.03 mol/l), H ₃ PO ₄ (0.06 mol/l)

Flow rate: 1.0 ml/min, detector: ultraviolet (UV) 270 nm

Using 0.5 mg of solvent relative to the polymer [THF/DMF = 1/1 (volume ratio)] A 1 ml solution was measured.

<Method for Measuring Content of NMP in Polymer Solution>

The polymer solution as a sample was diluted 10 times with DMF (N,N-dimethylformamide), and then injected into a gas chromatography (GC) apparatus to 1.0 μl and analyzed for NMP content. .

A calibration curve was prepared based on the NMP peak area of a standard solution having a NMP concentration of 0.02%, 0.2%, and 2% prepared by diluting NMP manufactured by Wako Pure Chemical Industries Co., Ltd. by DMF, and the peak area of the sample was determined. The content of NMP.

Specifically, the NMP content was measured by GC under the following apparatus and conditions.

Device: GL Science GC-4000

Carrier gas: 5.0ml/min

Column: TC-5

Injection temperature: 250 ° C

Detector temperature: 250 ° C

Oven temperature: 100 ° C (3 min) → 10 ° C / min → 250 ° C

<Method for Measuring Content of Chloride Ion in Polymer Solution>

The polymer solution was diluted to 1 to 1000 times with ion-exchanged water, and injected into 2 ml of ion chromatography (2010 I-6 manufactured by Dionex Co., Ltd.) to analyze the content of chloride ions. A calibration curve was prepared based on the peak height of Cl ions prepared by diluting a standard reagent (1000 ppm, manufactured by Wako Pure Chemical Industries, Ltd.) with an ion chromatograph of 5 ppm and 50 ppm standard solution, and the peak height of the sample was determined. The content of chloride ions.

<Method for Measuring Viscosity Change Rate>

The viscosity change rate was determined from the viscosity after initial production (initial viscosity) and the viscosity after storage for 2 weeks in a constant temperature bath (23 ° C) according to the following calculation formula.

Viscosity change rate (%) = (viscosity ÷ initial viscosity after 2 weeks of storage) × 100

The measurement of the viscosity was carried out under the following apparatus and conditions.

Measuring device: E-type viscometer (VISCONIC EHD of Toki Sangyo Co., Ltd.)

Measuring temperature: 25 ° C

Rotation speed: 2.5rpm~20rpm

<Synthesis of polymer mixture>

The step (a) of the present invention is carried out in the following manner to obtain a synthetic step of the polymer mixture.

Synthesis Example 1 [Synthesis of Polyimine Precursor Solution (Polymer Mixture A)]

3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (bis(3,4-dicarboxyphenyl) ether) in a 0.2 liter flask equipped with a stirrer and a thermometer Diacetate: ODPA)) 9.9 g (32 mmol) and isopropanol 3.9 g (65 mmol) were dissolved in 45 g of N-methylpyrrolidone. Thereafter, a catalyst amount of 1,8-diazabicycloundecene was added, followed by heating at 60 ° C for 2 hours. Then, the mixture was stirred at room temperature (25 ° C) for 15 hours to carry out esterification. Thereafter, 7.6 g (64 mmol) of sulfinium chloride was added thereto under ice cooling, and the reaction was returned to room temperature for 2 hours to obtain a solution of a carboxylic acid chloride ( This solution is referred to as a carboxylic acid chloride solution A).

Next, 40 g of N-methylpyrrolidone was added to a 0.5 liter flask equipped with a stirrer and a thermometer, and 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3 was further added. 3,3-hexafluoropropane 10.3 g (28 mmol) and p-aminophenol 0.4 g (4 mmol) were stirred and dissolved, and the temperature was maintained at 0 ° C to 5 ° C while the above-prepared carboxy group was added dropwise over 30 minutes. After the acid chloride solution A was stirred for 3 hours, a polymer mixture A was obtained.

Synthesis Example 2 [Synthesis of Polybenzoxazole Precursor Solution (Polymer Mixture B)]

To a 0.5 liter flask equipped with a stirrer and a thermometer, 15.5 g (60 mmol) of 4,4'-diphenylether dicarboxylic acid and 90 g of N-methylpyrrolidone were added, and the flask was cooled to 5 °C. Thereafter, 14.3 g (120 mmol) of sulfite chloride was added dropwise, and the mixture was reacted for 30 minutes to obtain a solution of 4,4'-diphenylether dicarboxylic acid dichloride.

Then, 88 g of N-methylpyrrolidone was added to a 1-liter flask equipped with a stirrer and a thermometer, and 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3 was added. 13.3 g (50 mmol) of 3,3-hexafluoropropane and 2.2 g (20 mmol) of p-aminophenol were stirred and dissolved. Thereafter, a solution of 4,4'-diphenylether dicarboxylic acid dichloride was added dropwise thereto over 30 minutes while maintaining the temperature at 0 ° C to 5 ° C, and the mixture was stirred for 3 hours to obtain a polymer mixture B.

Synthesis Example 3 [Synthesis of Polybenzoxazole Precursor (Polymer Mixture C)]

The polymer mixture C was obtained in the same manner as in Synthesis Example 2 except that the dodecyl dicarboxylic acid was used instead of the diphenyl ether dicarboxylic acid.

Synthesis Example 4 [Polybenzoxazole precursor solution (polymer mixture D) synthesis]

In a 0.2 liter flask equipped with a stirrer and a thermometer, 12.9 g (50 mmol) of 4,4'-diphenyl ether dicarboxylic acid and 13.5 g (100 mmol) of 1-hydroxybenzotriazole were dissolved in N-methyl-2. - Pyrrolidinone 75g. The temperature of the reaction system was cooled to 0 ° C to 5 ° C, and 1-ethyl-3-(3-dimethylaminopropyl) dissolved in 25 g of N-methyl-2-pyrrolidone was added dropwise thereto. The carbodiimide hydrochloride was 20.6 g (100 mmol). After completion of the dropwise addition, the temperature of the reaction system was returned to room temperature, and the mixture was stirred for 24 hours. After completion of the reaction, the precipitated dicyclohexylcarbodiurea was removed by filtration, and 100 g of ion-exchanged water was added dropwise to the filtrate, and the precipitate was collected by filtration and dried under vacuum. This is called a carboxylic acid derivative A.

2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane 12.8 g was dissolved in 90 g of N-methyl-2-pyrrolidone ( 35 mmol) and 1.5 g (14 mmol) of p-aminophenol were further added to 20.7 g (42 mmol) of the dicarboxylic acid derivative A, and the mixture was stirred and dissolved. Thereafter, the reaction system was brought to 75 ° C and stirred for 12 hours to obtain a polymer mixture D.

<Manufacture of polymer solution>

Example 1

(1) Step (b): liquid separation step

To 100 g of the polymer mixture A synthesized in Synthesis Example 1, 100 g of ethyl acetate as a low boiling point solvent and 100 g of ion-exchanged water were added, and liquid separation was carried out using a separator funnel. After the separatory funnel was shaken several times, it was left to stand still, and was divided into a low-boiling solvent layer and an aqueous layer, and then the water layer was removed.

Further, ion-exchanged water was further added to a separatory funnel containing a solvent layer having a low boiling point to carry out a liquid separation operation, and the aqueous layer was removed. The liquid separation operation of adding ion-exchanged water and removing the water layer was carried out 5 times.

(2) Step (c) and step (d)

To the obtained low boiling point solvent layer, 40 g of γ-butyrolactone (GBL) and 10 g of dimethyl hydrazine (DMSO) were added and mixed. Thereafter, the low-boiling solvent layer containing GBL and DMSO is concentrated under reduced pressure to remove ethyl acetate, and the concentration of the volatile component in the polymer solution is concentrated to about 65% or diluted with GBL. Polymer solution 1.

Further, the amount of the polymer precursor expected is calculated based on the amount of the raw material such as the monomer of the polymer precursor, and is a nonvolatile component (other than GBL and DMSO). The concentration of the volatile component in the polymer solution was determined by gas chromatography to quantify volatile components (GBL and DMSO).

The weight average molecular weight, the content of NMP, the content of chloride ions, and the rate of change in viscosity of the polymer solution 1 were determined by the above measurement methods. The polymer solution 1 had a weight average molecular weight of 12,760, an NMP content of 0.04%, a chloride ion content of 0.06%, and a viscosity change rate of 1.08%. The results are shown in Table 1.

Example 2

To the polymer mixture B (200 g) synthesized in Synthesis Example 2, ion-exchanged water (120 g) and methyl isobutyl ketone (MIBK) (120 g) as a low-boiling solvent were added, and The liquid separation step was carried out in the same manner as in Example 1.

The low boiling point obtained by the liquid separation step is dissolved in the same manner as in the first embodiment. GBL (60 g) and DMSO (12 g) were added to the layer and mixed. Thereafter, the low-boiling solvent layer containing GBL and DMSO is concentrated under reduced pressure to remove MIBK, and the concentration of the volatile component in the polymer solution is 65% or diluted with GBL to obtain a polymer solution. 2.

The obtained polymer solution was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 3

Polymer mixture B (200 g) was subjected to liquid separation in the same manner as in Example 2.

GBL (60 g) and N-ethylpyrrolidone (NEP) (12 g) were added to and mixed with the low boiling solvent layer obtained by the liquid separation step. Thereafter, the low-boiling solvent layer containing GBL and NEP is concentrated under reduced pressure to remove MIBK, and the concentration of the volatile component in the polymer solution is 65% or diluted with GBL to obtain a polymer solution. 3.

The obtained polymer solution was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 4

The same procedure as in Example 2 was carried out except that the polymer mixture liquid C synthesized in Synthesis Example 3 was used instead of the polymer mixture liquid B, and methyl tertiary butyl ether was used instead of MIBK as a low boiling point solvent. Liquid step.

GBL and N-ethylpyrrolidone (NEP) were added to and mixed with the low boiling solvent layer obtained by the liquid separation step. Thereafter, low boiling containing GBL and NEP The solvent layer was concentrated under reduced pressure to remove methyl tertiary butyl ether, and the concentration of the volatile component in the polymer solution was adjusted to 65% or diluted with GBL to obtain a polymer solution 4.

The obtained polymer solution was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 5

A polymer solution 5 was obtained by performing a liquid separation step or the like in the same manner as in Example 1 except that the polymer mixture liquid A was replaced with the polymer mixture liquid D synthesized in Synthesis Example 4.

The obtained polymer solution was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative example 1

The polymer mixture A synthesized in Synthesis Example 1 was placed in ion-exchange water, and the precipitate was recovered. The polyimide was sufficiently washed with ion-exchanged water and dried under reduced pressure to obtain a polyimide precursor (polyperurethane).

The recovered polyphthalate was dissolved in GBL so that the concentration of the volatile component in the polymer solution was 65%, and the polymer solution 6 was obtained.

The obtained polymer solution was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Comparative example 2

The polymer mixture B synthesized in Synthesis Example 2 was placed in ion-exchanged water, and the precipitate was recovered. Fully cleaned with ion-exchanged water for decompression Dry to obtain a polybenzoxazole precursor.

The recovered polybenzoxazole precursor was dissolved in GBL so that the concentration of the volatile component in the polymer solution became 65%, and the polymer solution 7 was obtained.

The obtained polymer solution was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Comparative example 3

The polymer mixture C synthesized in Synthesis Example 3 was placed in ion-exchanged water, and the precipitate was recovered. The mixture was sufficiently washed with ion-exchanged water and dried under reduced pressure to obtain a polybenzoxazole precursor having a carboxyl group at the end.

The recovered polybenzoxazole precursor was dissolved in GBL so that the concentration of the volatile component in the polymer solution became 65%, and the polymer solution 8 was obtained.

The obtained polymer solution was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Comparative example 4

The polymer mixture liquid D synthesized in Synthesis Example 4 was placed in a solution of a mixed solution of ion-exchanged water and isopropyl alcohol (ion-exchanged water/isopropyl alcohol = 3/1). The precipitate was recovered, washed thoroughly with ion-exchanged water, and dried under reduced pressure to obtain a polybenzoxazole precursor.

The recovered polybenzoxazole precursor was dissolved in GBL so that the concentration of the volatile component in the polymer solution became 65%, and the polymer solution 9 was obtained.

The obtained polymer solution was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 5

The polymer mixture A was subjected to liquid separation in the same manner as in Example 1.

GBL was added to the organic layer obtained by separation, and concentrated under reduced pressure to remove ethyl acetate, and the concentration of the volatile component in the polymer solution was adjusted to 65% or diluted with GBL to obtain a polymer solution 10. .

The obtained polymer solution was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 6

The polymer mixture B was subjected to liquid separation in the same manner as in Example 2.

GBL was added to the organic layer obtained by separation, and concentrated under reduced pressure to remove MIBK, and the concentration of the volatile component in the polymer solution was adjusted to 65% or diluted with GBL to obtain a polymer solution 11.

The obtained polymer solution was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 7

The polymer mixture C was subjected to liquid separation in the same manner as in Example 4.

GBL was added to the organic layer obtained by separation, and concentrated under reduced pressure to remove methyl tertiary butyl ether, and the concentration of the volatile component in the polymer solution was 65% or diluted with GBL. Polymer solution 12.

The obtained polymer solution was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 8

The polymer mixture D was subjected to liquid separation in the same manner as in Example 5.

GBL was added to the separated organic layer, and concentrated under reduced pressure to remove ethyl acetate, and the concentration of the volatile component in the polymer solution was adjusted to 65% or diluted with GBL to obtain a polymer solution. . The obtained polymer solution was evaluated by the same method as in Example 1. The results are shown in Table 2.

From the above results, it was confirmed that the polymer solution obtained by the method of the present invention has a lower NMP content and chloride ion content than the polymer solution obtained by the re-sinking operations of Comparative Examples 1 to 4.

Further, it was confirmed that a polymer solution excellent in viscosity stability can be obtained by adding a polar solvent.

From the above, by utilizing the present invention, an expansion of the field of use of a polyimide intermediate or a polybenzoxazole precursor solution can be expected.

[Industrial availability]

The polymer solution and the resin composition of the present invention are suitable for forming a cured film which is a surface protective film or an interlayer insulating film of an electronic component or the like.

The embodiments and/or the embodiments of the present invention have been described in detail above, but without departing from the novel teachings and effects of the present invention. It is easy to make various modifications to the illustrated embodiments and/or embodiments. Accordingly, such various modifications are intended to be included within the scope of the present invention.

The contents of the Japanese application specification which is the basis of the Paris priority of the present application are all incorporated herein by reference.

1‧‧‧Semiconductor substrate

2‧‧‧Protective film

3‧‧‧1st conductor layer

4‧‧‧Interlayer insulating film

5‧‧‧Photosensitive resin layer

6A, 6B, 6C‧‧‧ windows

7‧‧‧2nd conductor layer

8‧‧‧Surface protective film

Claims (10)

A method for producing a polymer solution comprising the following steps (a) to (d): (a) a synthesis step of causing an amine component and an acid component in a solvent comprising N-methyl-2-pyrrolidone (NMP) a reaction mixture to obtain a polymer mixture containing a polyimide precursor or a polybenzoxazole precursor; (b) a liquid separation step of adding water or an aqueous solution and a low boiling point solvent to the polymer mixture; The aqueous layer is removed by a liquid separation operation to obtain a low boiling point solvent layer; (c) a step of adding a replacement solvent and a polar solvent to the low boiling point solvent layer; (d) a concentration step, after the above step (c), The low boiling solvent is distilled off under reduced pressure. The method for producing a polymer solution according to claim 1, wherein the polar solvent is one or more selected from the group consisting of dimethyl hydrazine, N-ethyl pyrrolidone, and dimethylformamide. . The method for producing a polymer solution according to claim 1, wherein the low boiling point solvent is selected from the group consisting of isobutanol, ethyl acetate, butyl acetate, diethyl ether, methyl tert-butyl ether, and methyl group. One or more solvents of ethyl ketone and methyl isobutyl ketone. The method for producing a polymer solution according to claim 1, wherein the replacement solvent is one or more selected from the group consisting of γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether. Solvent. The method for producing a polymer solution according to claim 1, wherein the polyimine precursor or the polybenzoxazole precursor has a formula represented by the following formula (I) or formula (II) Structure, (In the formula (I), X represents a tetravalent organic group, p represents an integer of 0 to 2, and W is a divalent to tetravalent organic group; and R ¹ and R ² each independently represent a hydrogen atom, and the carbon number is 1~ An aliphatic group of 6 or a group represented by the following formula (Ia); (In the formula (Ia), R ³ is a hydrogen atom or a methyl group, and a represents an integer of 1 to 6) (In the formula (II), U is a tetravalent organic group, and V is a divalent organic group). A polymer solution obtained by the method for producing a polymer solution according to any one of claims 1 to 5. The polymer solution according to claim 6, wherein the content of the polar solvent is from 1% by mass to 20% by mass based on the whole. The polymer solution according to claim 6, wherein the content of the nonvolatile matter is from 10% by mass to 50% by mass based on the whole. A resin composition comprising the polymer solution according to any one of claims 6 to 8. A method for producing a cured film, comprising: applying a polymer solution according to any one of claims 6 to 8 or a resin composition according to claim 9 of the invention to a substrate And a step of drying to obtain a resin film; and a step of heating the resin film.