JP7435110B2 - Polyhydroxyimide, polymer solution, photosensitive resin composition and its uses - Google Patents

Description

The present invention relates to polyhydroxyimides, polymer solutions, photosensitive resin compositions, and uses thereof.

Polyimide resin has high mechanical strength, heat resistance, insulation properties, and solvent resistance, so it is widely used as a protective material for liquid crystal display elements and semiconductors, an insulating material, and a thin film for electronic materials such as color filters. .

Patent Document 1 discloses a positive photosensitive resin composition containing a hydroxy polyimide having a predetermined structure and a diazonaphthoquinone compound.
Patent Document 2 discloses a polyimide precursor containing an acid dianhydride, a diamine, and 1,3-bis(3-aminophenoxy)benzene.
Patent Documents 3 to 5 disclose photosensitive resin compositions containing polyimide precursors having a predetermined structure.

Patent Document 6 discloses a negative photosensitive resin precursor composition characterized by containing a polymer, a phenolic low molecular compound, a low molecular compound having a polymerizable group, and a photopolymerization initiator. ing.
Patent Document 7 discloses a positive photosensitive resin composition containing an organic solvent-soluble polyimide resin and an acid generator.

Japanese Patent Application Publication No. 2001-249454 Japanese Patent Application Publication No. 2013-241607 Japanese Patent Application Publication No. 2013-95894 Japanese Patent Application Publication No. 2014-172994 International Publication No. 2010/110335 Japanese Patent Application Publication No. 2004-133435 International Publication No. 2010/071100

However, in the conventional techniques described in Patent Documents 1 to 7, there is room for improvement in the mechanical strength of films containing polyimide obtained from photosensitive resin compositions.

Furthermore, when a film is prepared by coating and curing a photosensitive resin composition containing a polyimide precursor and an organic solvent, the dimensional stability of the film is affected by curing shrinkage when the polyimide precursor changes to polyimide. A photosensitive resin composition in which polyimide is dissolved in an organic solvent suppresses curing shrinkage of the resulting resin, but conventional polyimides have room for improvement in solubility in organic solvents.

The present inventors have discovered that the above-mentioned problems can be solved using polyhydroxyimide having a specific structure, and have completed the present invention.

（一般式（１）中、Ｘは単結合、－ＳＯ_２－、－Ｃ（＝Ｏ）－、炭素数１～５の直鎖または分岐のアルキレン基、または炭素数１～５の直鎖または分岐のフルオロアルキレン基を示し、複数存在するＸは同一でも異なっていてもよい。Ｙは下記一般式（１ａ）および下記一般式（１ｂ）で表される基から選択され、複数存在するＹは同一でも異なっていてもよい。ｎは平均値で２～５００の数である。）

（一般式（１ａ）中、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子、炭素数１～３のアルキル基、炭素数１～３のアルコキシ基を示し、複数存在するＲ^１同士、複数存在するＲ^２同士は同一でも異なっていてもよい。Ｒ^３は、水素原子、炭素数１～３のアルキル基、炭素数１～３のアルコキシ基を示し、複数存在するＲ^３同士は同一でも異なっていてもよい。一般式（１ｂ）中、Ｒ^４およびＲ^５は、それぞれ独立して、水素原子、炭素数１～３のアルキル基、炭素数１～３のアルコキシ基を示し、複数存在するＲ^４同士、複数存在するＲ^５同士は同一でも異なっていてもよい。＊は結合手を示す。）
本発明によれば、前記ポリヒドロキシイミドと有機溶媒とを含むポリマー溶液を提供することができる。
本発明によれば、前記ポリヒドロキシイミドと、架橋剤と、感光剤と、を含む、感光性樹脂組成物を提供することができる。
本発明によれば、前記感光性樹脂組成物の硬化物で構成される硬化膜を提供することができる。
本発明によれば、前記感光性樹脂組成物の硬化物を含む樹脂膜を備える半導体装置を提供することができる。
本発明によれば、下記一般式（ａ）で表されるビスアミノフェノールと、下記一般式（ｂ）で表される酸無水物とを、１００℃以上２５０℃以下の温度下でイミド化する工程を含む、一般式（１）で表されるポリヒドロキシイミドの製造方法を提供することができる。

（一般式（ａ）中、Ｘは単結合、－ＳＯ_２－、－Ｃ（＝Ｏ）－、炭素数１～５の直鎖または分岐のアルキレン基、または炭素数１～５の直鎖または分岐のフルオロアルキレン基を示す。）

（一般式（ｂ）中、Ｙは下記一般式（１ａ）および（１ｂ）で表される基から選択される。）

（一般式（１ａ）中、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子、炭素数１～３のアルキル基、炭素数１～３のアルコキシ基を示し、複数存在するＲ^１同士、複数存在するＲ^２同士は同一でも異なっていてもよい。Ｒ^３は、水素原子、炭素数１～３のアルキル基、炭素数１～３のアルコキシ基を示し、複数存在するＲ^３同士は同一でも異なっていてもよい。一般式（１ｂ）中、Ｒ^４およびＲ^５は、それぞれ独立して、水素原子、炭素数１～３のアルキル基、炭素数１～３のアルコキシ基を示し、複数存在するＲ^４同士、複数存在するＲ^５同士は同一でも異なっていてもよい。＊は結合手を示す。）

（一般式（１）中、Ｘは一般式（ａ）と同義であり、Ｙは一般式（ｂ）と同義である。ｎは平均値で２～５００の数である。） According to the present invention, a polyhydroxyimide represented by the following general formula (1) can be provided.

(In general formula (1), X is a single bond, -SO ₂ -, -C(=O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or It represents a branched fluoroalkylene group, and multiple X's may be the same or different.Y is selected from the groups represented by the following general formula (1a) and the following general formula (1b), and the multiple Y's are They may be the same or different. n is an average value of 2 to 500.)

(In general formula (1a), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ^1s exist, A plurality of R ^2s may be the same or different. R ³ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbons, and a plurality of R ^3s may be the same. In the general formula (1b), R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and Existing R ^4s and multiple R ^5s may be the same or different. * indicates a bond.)
According to the present invention, a polymer solution containing the polyhydroxyimide and an organic solvent can be provided.
According to the present invention, it is possible to provide a photosensitive resin composition containing the polyhydroxyimide, a crosslinking agent, and a photosensitizer.
According to the present invention, it is possible to provide a cured film composed of a cured product of the photosensitive resin composition.
According to the present invention, it is possible to provide a semiconductor device including a resin film containing a cured product of the photosensitive resin composition.
According to the present invention, a bisaminophenol represented by the following general formula (a) and an acid anhydride represented by the following general formula (b) are imidized at a temperature of 100°C or higher and 250°C or lower. It is possible to provide a method for producing a polyhydroxyimide represented by the general formula (1), including the steps.

(In general formula (a), X is a single bond, -SO ₂ -, -C(=O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or (Indicates a branched fluoroalkylene group.)

(In the general formula (b), Y is selected from the groups represented by the following general formulas (1a) and (1b).)

(In general formula (1a), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ^1s exist, A plurality of R ^2s may be the same or different. R ³ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbons, and a plurality of R ^3s may be the same. In the general formula (1b), R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; Existing R ^4s and multiple R ^5s may be the same or different. * indicates a bond.)

(In general formula (1), X has the same meaning as general formula (a), and Y has the same meaning as general formula (b). n is a number from 2 to 500 as an average value.)

The polyhydroxyimide of the present invention can be used to obtain cured products such as films with excellent mechanical strength, and is dimensionally stable because it has excellent solubility in solvents and does not need to be made into a varnish in the precursor state. A cured product such as a film with excellent properties can be obtained.

1 is a schematic cross-sectional view of a semiconductor device of this embodiment. 3 is a strain-stress curve of a film made of the polymer solution obtained in Example 3.

Embodiments of the present invention will be described below with reference to the drawings. Note that in all the drawings, similar components are denoted by the same reference numerals, and descriptions thereof will be omitted as appropriate. In addition, "~" represents "more than" to "less than" unless otherwise specified.

<Polyhydroxyimide>
The polyhydroxyimide of this embodiment is represented by the following general formula (1).

In the general formula ( ₁ ), represents a fluoroalkylene group, and multiple Xs may be the same or different.
From the viewpoint of the effects of the present invention, X is preferably a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or branched fluoroalkylene group having 1 to 5 carbon atoms.

Y is selected from the groups represented by the following general formula (1a) and the following general formula (1b), and a plurality of Y's may be the same or different.
n is a number from 2 to 500 on average.

In the general formula (1a), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to ³ carbon atoms; The ^R2s present may be the same or different.
From the viewpoint of the effects of the present invention, R ¹ and R ² are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

R ³ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ^3s may be the same or different.
From the viewpoint of the effects of the present invention, R ³ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

In general formula (1b), R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or ^an alkoxy group having 1 to 3 carbon atoms; The R ^5s present may be the same or different.
From the viewpoint of the effect of the present invention, R ⁴ and R ⁵ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably at least one of R ⁴ and at least one of R ⁵ has a carbon number of 1 to 3. 1 to 3 alkyl groups, more preferably three R ⁴ are alkyl groups having 1 to 3 carbon atoms, one R ⁴ is a hydrogen atom, and three R ⁵ are alkyl groups having 1 to 3 carbon atoms. group in which one R ⁵ is a hydrogen atom, particularly preferably three R ⁴ are a methyl group and one R ⁴ is a hydrogen atom, and three R ⁵ are a methyl group and one R ⁵ is a hydrogen atom. A hydrogen atom appears.
* indicates a bond.

In the present embodiment, as the polyhydroxyimide represented by the general formula (1), X represents -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -,
Y is a group in which R ¹ , R ² and R ³ in the general formula (1a) are hydrogen atoms, or a group in which R ⁴ and R ⁵ in the general formula (1b) are hydrogen atoms or an alkyl group having 1 to 3 carbon atoms; represents a group in which at least one of R ⁴ and at least one of R ⁵ is an alkyl group having 1 to 3 carbon atoms,
A combination is preferred.
With this combination, it is possible to provide a film with even better mechanical strength.

The weight average molecular weight of the polyhydroxyimide of this embodiment is 10,000 to 300,000, preferably 20,000 to 200,000.

The polyhydroxyimide of this embodiment having this structure can provide a film with excellent mechanical strength. The reason for this is not clear, but it is presumed that strong packing between polymer chains suppresses breakage due to polymer chains slipping through, improving elongation and providing excellent flexibility.
In addition, the polyhydroxyimide of this embodiment has excellent solubility in a solvent and does not need to be made into a varnish in a precursor state, so a varnish containing polyhydroxyimide can be prepared, and from the varnish. A cured product such as a film with excellent dimensional stability can be obtained.

<Production method of polyhydroxyimide>
The method for producing polyhydroxyimide represented by general formula (1) of this embodiment is as follows:
The method includes a step of imidizing a bisaminophenol represented by the following general formula (a) and an acid anhydride represented by the following general formula (b) at a temperature of 100°C or higher and 250°C or lower.
According to this embodiment, polyhydroxyimide having excellent solubility in organic solvents can be synthesized by a simple method.

In general formula (a), X has the same meaning as in general formula (1).

In the general formula (b), Y is selected from groups represented by the following general formulas (1a) and (1b).

In general formula (1a), R ¹ , R ² and R ³ have the same meanings as R ¹ , R ² and R ³ in general formula (1a) in Y of general formula (1), and in general formula (1b) , R ⁴ and R ⁵ have the same meanings as R ⁴ and R ⁵ in general formula (1b) in Y of general formula (1). * indicates a bond.

In order to control the molecular weight of the resulting polyhydroxyimide, it is also possible to carry out the reaction by adding a small amount of acid anhydride or aromatic amine as an end capping agent.
Examples of the acid anhydride as an end capping agent include phthalic anhydride, maleic anhydride, nadic anhydride, etc., and examples of the aromatic amine include p-methylaniline, p-methoxyaniline, p-phenoxyaniline, etc. The amount of acid anhydride or aromatic amine added as an end capping agent is preferably 5 mol % or less. If it exceeds 5 mol %, the molecular weight of the polyhydroxyimide obtained will decrease significantly, causing problems in heat resistance and mechanical properties.

The equivalent ratio of acid anhydride and bisaminophenol in the imidization reaction is an important factor that determines the molecular weight of the resulting polyhydroxyimide. Generally, it is well known that there is a correlation between the molecular weight and mechanical properties of a polymer, and the larger the molecular weight, the better the mechanical properties. Therefore, in order to obtain a polyhydroxyimide with practically excellent strength, it is necessary to have a certain degree of high molecular weight. In the present invention, the equivalent ratio of acid anhydride to bis-aminophenol used is not particularly limited, but it is preferable that the equivalent ratio of acid anhydride to bis-aminophenol is in the range of 0.90 to 1.06. If it is less than 0.90, the molecular weight is low and brittle, resulting in weak mechanical strength. Moreover, if it exceeds 1.06, unreacted carboxylic acid may decarboxylate during heating, causing gas generation and foaming, which may be undesirable.
In addition, from the viewpoint of improving mechanical properties, even if the equivalent ratio of acid anhydride to bisaminophenol is out of the above range, the apparent molecular weight can be increased by side chain crosslinking of the resin.

The step (imidization reaction step) can be performed in an organic solvent by a known method.
Examples of organic solvents include aprotic polar solvents such as γ-butyllactone (GBL), N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, cyclohexanone, and 1,4-dioxane. These types may be used alone or in combination of two or more types. At this time, a non-polar solvent that is compatible with the above-mentioned aprotic polar solvent may be used in combination. Examples of non-polar solvents include aromatic hydrocarbons such as toluene, ethylbenzene, xylene, mesitylene, and solvent naphtha. The proportion of non-polar solvent in the mixed solvent can be set arbitrarily depending on the resin properties such as stirring device capacity and solution viscosity, as long as the solubility of the solvent decreases and the polyamic acid resin obtained by reaction does not precipitate. can do.

The reaction temperature is 0°C to 100°C, preferably 20°C to 80°C for about 30 minutes to 2 hours, and then 100°C to 250°C, preferably 120°C to 200°C for 1 to 5 hours. Let it react for about an hour.

Through the above steps, a reaction solution containing the polyhydroxyimide of this embodiment can be obtained, and if necessary, it can be diluted with an organic solvent or the like and used as a polymer solution (varnish for coating). As the organic solvent, those exemplified in the reaction step can be used, and it may be the same organic solvent as in the reaction step or a different organic solvent.
Alternatively, this reaction solution may be poured into a poor solvent to reprecipitate the polyimide resin to remove unreacted monomers, dry and solidify the resulting product, which can be redissolved in an organic solvent and used as a purified product. Particularly in applications where impurities and foreign substances are a problem, it is preferable to dissolve the varnish again in an organic solvent to obtain a filtration-purified varnish.

The concentration of polyhydroxyimide in the polymer solution (100% by weight) is not particularly limited, but is approximately 10 to 30% by weight.

<Photosensitive resin composition>
The photosensitive resin composition of this embodiment includes the above-mentioned polyhydroxyimide, a crosslinking agent, and a photosensitizer. Polyhydroxyimide can be added as a polymer solution (varnish).

(Crosslinking agent)
The photosensitive resin composition according to the present embodiment includes a crosslinking agent (thermal crosslinking agent) that can react with polyhydroxyimide by heat. Thereby, mechanical properties such as tensile elongation at break can be improved in a cured product obtained by post-baking the photosensitive resin composition. It is also preferable from the viewpoint of improving the sensitivity of the resin film formed from the photosensitive resin composition.

Specific examples of the crosslinking agent include 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol (paraxylene glycol), 1,3,5-benzenedimethanol, 4 , 4-biphenyl dimethanol, 2,6-pyridine dimethanol, 2,6-bis(hydroxymethyl)-p-cresol, 4,4'-methylenebis(2,6-dialkoxymethylphenol), etc. A compound having;
Phenols such as phlorogluside; 1,4-bis(methoxymethyl)benzene, 1,3-bis(methoxymethyl)benzene, 4,4'-bis(methoxymethyl)biphenyl, 3,4'-bis(methoxymethyl) Compounds having an alkoxymethyl group such as biphenyl, 3,3'-bis(methoxymethyl)biphenyl, methyl 2,6-naphthalene dicarboxylate, and 4,4'-methylenebis(2,6-dimethoxymethylphenol);
Methylolmelamine compounds represented by hexamethylolmelamine, hexabutanolmelamine, etc.;
Alkoxymelamine compounds such as hexamethoxymelamine;
alkoxymethyl glycoluril compounds such as tetramethoxymethyl glycoluril;
Methylolurea compounds such as methylolbenzoguanamine compounds and dimethylolethyleneurea;
Cyano compounds such as dicyanoaniline, dicyanophenol, cyanophenylsulfonic acid;
Isocyanate compounds such as 1,4-phenylene diisocyanate and 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate;
Containing epoxy groups such as ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, triglycidyl isocyanurate, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, phenol novolak resin type epoxy resin Compound;
Examples include maleimide compounds such as N,N'-1,3-phenylene dimaleimide and N,N'-methylene dimaleimide. As the thermal crosslinking agent, one or a combination of two or more of the above specific examples can be used.

The upper limit of the content of the thermal crosslinking agent in the photosensitive resin composition is preferably, for example, 50 parts by mass or less, more preferably 30 parts by mass or less, based on 100 parts by mass of polyhydroxyimide. , more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less. Thereby, even when the thermal crosslinking agent includes a solvating functional group such as a phenolic hydroxyl group, it is possible to suppress a decrease in chemical resistance after post-baking.

Further, the lower limit of the content of the thermal crosslinking agent in the photosensitive resin composition is, for example, preferably 0.1 part by mass or more, and 1 part by mass or more, based on 100 parts by mass of polyhydroxyimide. The amount is more preferably 3 parts by weight or more, even more preferably 5 parts by weight or more, and particularly preferably 8 parts by weight or more.

(Photosensitizer)
As the photosensitizer, a photoacid generator that generates acid by absorbing light energy can be used.

Specific examples of photoacid generators include diazoquinone compounds; diaryliodonium salts; 2-nitrobenzyl ester compounds; N-iminosulfonate compounds; imidosulfonate compounds; 2,6-bis(trichloromethyl)-1,3, Examples include 5-triazine compounds; dihydropyridine compounds. Among these, it is preferable to use photosensitive diazoquinone compounds. Thereby, the sensitivity of the photosensitive resin composition can be improved. Therefore, the accuracy of the pattern can be improved and the appearance can be improved. Note that the photoacid generator may include one or more of the above specific examples.

Further, when the photosensitive resin composition is positive type, in addition to the above-mentioned specific examples, onium salts such as triarylsulfonium salts and sulfonium borate salts may also be used as photosensitizers. Thereby, the sensitivity of the photosensitive resin composition can be further improved.
Specific examples of diazoquinone compounds that can be preferably used as photosensitizers are shown below.

n is an integer of 1 or more and 5 or less.

In each of the above diazoquinone compounds, Q is a structure represented by the following formula (a), the following formula (b), or the following formula (c), or a hydrogen atom. However, at least one of Q in each diazoquinone compound has a structure represented by the following formula (a), the following formula (b), and the following formula (c).

It is preferable that Q of the diazoquinone compound includes the following formula (a) or the following formula (b). Thereby, the transparency of the photosensitive resin composition can be improved. Therefore, the appearance of the photosensitive resin composition can be improved.

The lower limit of the content of the photosensitizer in the photosensitive resin composition is, for example, preferably 1 part by mass or more, more preferably 3 parts by mass or more when the polyhydroxyimide is 100 parts by mass. , more preferably 5 parts by mass or more. Thereby, the photosensitive resin composition can exhibit appropriate sensitivity.

Further, the upper limit of the content of the photosensitizer in the photosensitive resin composition is preferably 30 parts by mass or less, and preferably 20 parts by mass or less, when the polyhydroxyimide is 100 parts by mass. More preferred. Thereby, the photosensitive resin composition can be appropriately cured and exhibit adhesion to metals such as Al and Cu after pre-baking and post-baking.

(solvent)
The photosensitive resin composition according to the present embodiment can contain a urea compound or an amide compound with an acyclic structure as a solvent. The solvent preferably contains, for example, a urea compound. Thereby, the adhesiveness between the cured product of the photosensitive resin composition and metals such as Al and Cu can be further improved.

In addition, in this specification, a urea compound refers to a urea bond, that is, a compound having a urea bond. Moreover, the amide compound refers to a compound having an amide bond, that is, an amide. Note that amide specifically includes primary amide, secondary amide, and tertiary amide.

Furthermore, in the present embodiment, an acyclic structure means that the structure of the compound does not include a cyclic structure such as a carbocyclic ring, an inorganic ring, or a heterocyclic ring. Examples of the structure of a compound without a cyclic structure include a linear structure and a branched structure.

As the urea compound and the amide compound having a non-cyclic structure, those having a large number of nitrogen atoms in the molecular structure are preferable. Specifically, it is preferable that the number of nitrogen atoms in the molecular structure is two or more. Thereby, the number of lone electron pairs can be increased. Therefore, adhesion to metals such as Al and Cu can be improved.

Specific examples of the structure of the urea compound include a cyclic structure and an acyclic structure. Among the above specific examples, the structure of the urea compound is preferably an acyclic structure. Thereby, the adhesiveness between the cured product of the photosensitive resin composition and metals such as Al and Cu can be improved. The reason for this is assumed to be as follows. It is presumed that urea compounds with a non-cyclic structure form coordinate bonds more easily than urea compounds with a cyclic structure. This is thought to be because urea compounds with a non-cyclic structure have less constraint on molecular movement and have a greater degree of freedom in deforming the molecular structure than urea compounds with a cyclic structure. Therefore, when a urea compound with an acyclic structure is used, a strong coordinate bond can be formed and adhesion can be improved.

Specifically, the urea compounds include tetramethylurea (TMU), 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacetamide, tetrabutylurea, N,N'-dimethylpropyleneurea, 1, 3-dimethoxy-1,3-dimethylurea, N,N'-diisopropyl-O-methylisourea, O,N,N'-triisopropylisourea, O-tert-butyl-N,N'-diisopropylisourea, Examples include O-ethyl-N,N'-diisopropylisourea and O-benzyl-N,N'-diisopropylisourea. As the urea compound, one or a combination of two or more of the above specific examples can be used. Examples of the urea compound include, among the above specific examples, tetramethylurea (TMU), tetrabutylurea, 1,3-dimethoxy-1,3-dimethylurea, N,N'-diisopropyl-O-methylisourea, O,N , N'-triisopropylisourea, O-tert-butyl-N,N'-diisopropylisourea, O-ethyl-N,N'-diisopropylisourea and O-benzyl-N,N'-diisopropylisourea It is preferable to use one or more types selected from the group consisting of: Tetramethylurea (TMU) is more preferably used. Thereby, a strong coordinate bond can be formed and adhesion can be improved.

Specifically, the amide compound having a non-cyclic structure includes 3-methoxy-N,N-dimethylpropanamide, N,N-dimethylformamide, N,N-dimethylpropionamide, N,N-diethylacetamide, 3-methoxy-N-dimethylpropanamide, N,N-dimethylformamide, N,N-dimethylpropionamide, Examples include butoxy-N,N-dimethylpropanamide and N,N-dibutylformamide.

The photosensitive resin composition according to the present embodiment may contain, as a solvent, a solvent that does not have a nitrogen atom, in addition to a urea compound and an amide compound with an acyclic structure.

Examples of solvents without nitrogen atoms include ether solvents, acetate solvents, alcohol solvents, ketone solvents, lactone solvents, carbonate solvents, sulfone solvents, ester solvents, and aromatic hydrocarbons. Examples include solvents. As the solvent without a nitrogen atom, one type or a combination of two or more types of the above specific examples can be used.

Specifically, the above ether solvents include propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol, ethylene glycol diethyl ether, and diethylene glycol diethyl ether. , diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, 1,3-butylene glycol-3-monomethyl ether, and the like.

Specific examples of the acetate solvent include propylene glycol monomethyl ether acetate (PGMEA), methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, and the like.

Specific examples of the alcoholic solvent include tetrahydrofurfuryl alcohol, benzyl alcohol, 2-ethylhexanol, butanediol, and isopropyl alcohol.
Specific examples of the ketone solvent include cyclopentanone, cyclohexanone, diacetone alcohol, and 2-heptanone.
Specific examples of the lactone solvent include γ-butyrolactone (GBL) and γ-valerolactone.
Specific examples of the carbonate solvent include ethylene carbonate, propylene carbonate, and the like.
Specific examples of the sulfone solvent include dimethyl sulfoxide (DMSO) and sulfolane.
Specific examples of the ester solvent include methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, and the like.
Specific examples of the aromatic hydrocarbon solvent include mesitylene, toluene, xylene, and the like.

The lower limit of the content of the urea compound and the acyclic structure amide compound in the solvent is, for example, preferably 10 parts by mass or more, and preferably 20 parts by mass or more when the solvent is 100 parts by mass. The amount is more preferably 30 parts by mass or more, even more preferably 50 parts by mass or more, and even more preferably 70 parts by mass or more. Thereby, the adhesiveness between the cured product of the photosensitive resin composition and metals such as Al and Cu can be further improved.

Further, the lower limit of the content of the urea compound and the amide compound having an acyclic structure in the solvent can be, for example, 100 parts by mass or less when the solvent is 100 parts by mass. It is preferable from the viewpoint of improving adhesion that the content of the urea compound and the amide compound having an acyclic structure is large in the solvent.

(surfactant)
The photosensitive resin composition according to this embodiment may further contain a surfactant.

Surfactants are not limited, and specifically include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene Polyoxyethylene aryl ethers such as nonylphenyl ether; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; FTOP EF301, FTOP EF303, FTOP EF352 (Manufactured by Shin-Akita Kasei Co., Ltd.), Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F444, Megafac F470, Megafac F471, Megafac F475, Megafac F482, Megafac F477 (DIC) ), Florado FC-430, Florado FC-431, Novec FC4430, Novec FC4432 (manufactured by 3M Japan), Surflon S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Fluorine-based surfactants commercially available under names such as Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (manufactured by AGC Seimi Chemical Co., Ltd.); organosiloxane copolymer Combined KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); (meth)acrylic acid copolymer Polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

Among these, it is preferable to use a fluorine-based surfactant having a perfluoroalkyl group. Examples of the fluorine-based surfactant having a perfluoroalkyl group include Megafac F171, Megafac F173, Megafac F444, Megafac F470, Megafac F471, Megafac F475, Megafac F482, and Megafac F482 among the above specific examples. One or more types selected from F477 (manufactured by DIC), Surflon S-381, Surflon S-383, Surflon S-393 (manufactured by AGC Seimi Chemical), Novec FC4430, and Novec FC4432 (manufactured by 3M Japan) It is preferable to use

Furthermore, as the surfactant, silicone surfactants (eg, polyether-modified dimethylsiloxane, etc.) can also be preferably used. Specific examples of silicone surfactants include the SH series, SD series, and ST series from Dow Corning Toray, the BYK series from BYK Chemie Japan, the KP series from Shin-Etsu Chemical Co., Ltd., and the Disform series from NOF Corporation. (registered trademark) series, TSF series of Toshiba Silicone Co., Ltd., and the like.

The upper limit of the content of the surfactant in the photosensitive resin composition is preferably 1% by mass (10,000 ppm) or less with respect to the entire photosensitive resin composition (including the solvent), and 0.5% by mass % (5000 ppm) or less, and even more preferably 0.1 mass % (1000 ppm) or less.

Furthermore, although there is no particular lower limit for the content of the surfactant in the photosensitive resin composition, from the viewpoint of obtaining sufficient effects from the surfactant, for example, the entire photosensitive resin composition (solvent 0.001% by mass (10ppm) or more based on the amount of
By appropriately adjusting the amount of surfactant, it is possible to improve coatability and uniformity of the coating film while maintaining other properties.

(Antioxidant)
The photosensitive resin composition according to this embodiment may further contain an antioxidant. As the antioxidant, one or more selected from phenolic antioxidants, phosphorus antioxidants, and thioether antioxidants can be used. The antioxidant can suppress oxidation of the resin film formed by the photosensitive resin composition.

Examples of phenolic antioxidants include pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,9-bis{2-[3-(3 -t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}2,4,8,10-tetraoxaspiro[5,5]undecane, octadecyl-3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate, 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,3,5 -trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t -butyl-4-ethylphenol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-t-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-t- -butyl-4-hydroxybenzyl)phosphonate, thiodiethylene glycol bis[(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 4,4'-thiobis(6-t-butyl-m-cresol) , 2-octylthio-4,6-di(3,5-di-t-butyl-4-hydroxyphenoxy)-s-triazine, 2,2'-methylenebis(4-methyl-6-t-butyl-6- butylphenol), 2,-2'-methylenebis(4-ethyl-6-t-butylphenol), bis[3,3-bis(4-hydroxy-3-t-butylphenyl)butyric acid] glycol ester, 4, 4'-butylidenebis(6-t-butyl-m-cresol), 2,2'-ethylidenebis(4,6-di-t-butylphenol), 2,2'-ethylidenebis(4-s-butyl-6 -t-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, bis[2-t-butyl-4-methyl-6-(2-hydroxy- 3-t-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris[(3,5-di-t-butyl-4-hydroxyphenyl) Propionyloxyethyl]isocyanurate, Tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 2-t-butyl-4-methyl-6-(2-acryloyloxy) -3-tert-butyl-5-methylbenzyl)phenol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4-8,10-tetraoxaspiro[5,5]undecane- Bis[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], triethylene glycol bis[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], 1,1'-bis(4-hydroxyphenyl)cyclohexane, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,2'-methylenebis(6-(1-methylcyclohexyl)-4-methylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 3,9-bis(2-(3 -t-butyl-4-hydroxy-5-methylphenylpropionyloxy)1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, 4,4'-thiobis(3 -methyl-6-t-butylphenol), 4,4'-bis(3,5-di-t-butyl-4-hydroxybenzyl) sulfide, 4,4'-thiobis(6-t-butyl-2-methyl) phenol), 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)- Examples include 4-methylphenyl acrylate, 2,4-dimethyl-6-(1-methylcyclohexyl, styrenated phenol, 2,4-bis((octylthio)methyl)-5-methylphenol), and the like.

Examples of phosphorus antioxidants include bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, tris(2,4-di-t-butylphenylphosphite), and tetrakis(2-di-t-butylphenylphosphite). , 4-di-t-butyl-5-methylphenyl)-4,4'-biphenylene diphosphonite, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, bis-(2,6 -dicumylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite, tris(mixed mono and di-nonylphenylphosphite), bis(2, 4-di-t-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methoxycarbonylethyl-phenyl) pentaerythritol diphosphite, bis(2,6-di-t -butyl-4-octadecyloxycarbonylethylphenyl) pentaerythritol diphosphite and the like.

Examples of thioether antioxidants include dilauryl-3,3'-thiodipropionate and bis(2-methyl-4-(3-n-dodecyl)thiopropionyloxy)-5-t-butylphenyl) sulfide. , distearyl-3,3'-thiodipropionate, pentaerythritol-tetrakis(3-lauryl)thiopropionate, and the like.

(filler)
The photosensitive resin composition according to this embodiment may further contain a filler. As the filler, an appropriate filler can be selected depending on the mechanical properties and thermal properties required of the resin film made of the photosensitive resin composition.
Specific examples of the filler include inorganic fillers and organic fillers.

Specifically, the inorganic fillers include silica such as fused crushed silica, fused spherical silica, crystalline silica, secondary agglomerated silica, and finely powdered silica; alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, and silicon carbide. , metal compounds such as aluminum hydroxide, magnesium hydroxide, and titanium white; talc; clay; mica; and glass fiber. As the inorganic filler, one or a combination of two or more of the above specific examples can be used.

Specific examples of the organic filler include organosilicone powder, polyethylene powder, and the like. As the organic filler, one or a combination of two or more of the above specific examples can be used.

(Preparation of photosensitive resin composition)
The method for preparing the photosensitive resin composition in this embodiment is not limited, and any known method can be used depending on the components contained in the photosensitive resin composition.
For example, it can be prepared by mixing and dissolving the above components in a solvent.

(Photosensitive resin composition)
The photosensitive resin composition according to the present embodiment is prepared by applying the photosensitive resin composition to a surface containing a metal such as Al or Cu, and then drying it by prebaking to form a resin film. It is used by patterning the resin film into a desired shape by exposure and development, and then hardening the resin film by post-baking to form a cured film.

In addition, when producing the above-mentioned permanent film, the prebaking conditions may be, for example, a heat treatment at a temperature of 90° C. or more and 130° C. or less for 30 seconds or more and 1 hour or less. Further, the post-baking conditions may be, for example, heat treatment at a temperature of 150° C. or higher and 350° C. or lower for 30 minutes or more and 10 hours or less.

The viscosity of the photosensitive resin composition according to this embodiment can be appropriately set depending on the desired thickness of the resin film. The viscosity of the photosensitive resin composition can be adjusted by adding a solvent. In addition, during adjustment, it is necessary to keep the contents of the urea compound and the amide compound with a non-cyclic structure constant in the solvent.

The upper limit of the viscosity of the photosensitive resin composition according to the present embodiment may be, for example, 2000 mPa·s or less, 1800 mPa·s or less, or 1500 mPa·s or less. Further, the lower limit of the viscosity of the photosensitive resin composition according to the present embodiment may be, for example, 10 mPa·s or more, or 50 mPa·s or more, depending on the desired thickness of the resin film.

The film (resin film) obtained from the photosensitive resin composition or polymer solution of this embodiment has a maximum elongation rate of 30 to 200%, preferably 50 to 150%, as measured by a tensile test using a Tensilon tester. The average value is 15 to 150%, preferably 20 to 100%.

The film obtained from the photosensitive resin composition or polymer solution of this embodiment can have a tensile strength of 30 to 300 MPa, preferably 50 to 200 MPa.

In this way, the polyhydroxyimide of this embodiment can provide a cured product such as a film with excellent mechanical strength. The reason for this is not clear, but it is presumed that strong packing between polymer chains suppresses breakage due to polymer chains slipping through, improving elongation and providing excellent flexibility.

The polyhydroxyimide of this embodiment has suppressed curing shrinkage, and the film made of the polyhydroxyimide has a weight loss temperature (Td5) of 200°C or higher, preferably 300°C, as measured by simultaneous thermogravimetric differential thermal measurement. It can be more than that.

The film made of polyhydroxyimide of this embodiment has suppressed curing shrinkage, and has a coefficient of linear thermal expansion (CTE) of 200 ppm, preferably 100 ppm or less.

(Application)
The photosensitive resin composition of this embodiment is used to form a resin film for semiconductor devices, such as a permanent film or a resist. Among these, from the viewpoint of improving the adhesion between the photosensitive resin composition and the Al pad after pre-baking and suppressing the generation of residues of the photosensitive resin composition during development in a well-balanced manner, the photosensitive resin after post-baking From the viewpoint of improving the adhesion between the cured film of the composition and the metal, as well as improving the chemical resistance of the photosensitive resin composition after post-baking, it is preferably used in applications using a permanent film. .

Note that in this embodiment, the resin film includes a cured film of a photosensitive resin composition. That is, the resin film according to this embodiment is formed by curing a photosensitive resin composition.

The permanent film is a resin film obtained by pre-baking, exposing and developing a photosensitive resin composition, patterning it into a desired shape, and then curing it by post-baking. The permanent film can be used as a protective film, an interlayer film, a dam material, etc. for semiconductor devices.

The above-mentioned resist can be prepared by applying a photosensitive resin composition to an object to be masked by the resist using a method such as spin coating, roll coating, flow coating, dip coating, spray coating, or doctor coating. It consists of a resin film obtained by removing the solvent from.

FIG. 1 shows an example of a semiconductor device according to this embodiment.
The semiconductor device 100 according to this embodiment can be a semiconductor device including the resin film described above. Specifically, in the semiconductor device 100, one or more of the group consisting of the passivation film 32, the insulating layer 42, and the insulating layer 44 can be a resin film containing the cured product of this embodiment. Here, the resin film is preferably the above-mentioned permanent film.

The semiconductor device 100 is, for example, a semiconductor chip. In this case, for example, a semiconductor package is obtained by mounting the semiconductor device 100 on a wiring board via the bumps 52.

The semiconductor device 100 includes a semiconductor substrate provided with semiconductor elements such as transistors, and a multilayer wiring layer (not shown) provided on the semiconductor substrate. An interlayer insulating film 30 and an uppermost layer wiring 34 provided on the interlayer insulating film 30 are provided in the uppermost layer of the multilayer wiring layer. The uppermost layer wiring 34 is made of aluminum Al, for example. Further, a passivation film 32 is provided on the interlayer insulating film 30 and the uppermost layer wiring 34. A part of the passivation film 32 is provided with an opening through which the uppermost layer wiring 34 is exposed.

A rewiring layer 40 is provided on the passivation film 32. The rewiring layer 40 includes an insulating layer 42 provided on the passivation film 32, a rewiring 46 provided on the insulating layer 42, an insulating layer 44 provided on the insulating layer 42 and the rewiring 46, has. An opening connected to the uppermost layer wiring 34 is formed in the insulating layer 42 . The rewiring 46 is formed on the insulating layer 42 and in an opening provided in the insulating layer 42, and is connected to the uppermost layer wiring 34. The insulating layer 44 is provided with an opening connected to the rewiring 46 .

A bump 52 is formed in the opening provided in the insulating layer 44 via, for example, a UBM (Under Bump Metallurgy) layer 50 . The semiconductor device 100 is connected to a wiring board or the like via bumps 52, for example.

Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be adopted within a range that does not impair the effects of the present invention.

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.
In the examples, the following compounds were used.

2,2-bis(3-amino-4-hydroxyphenyl)propane (hereinafter also referred to as BAP) represented by the following formula

2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter also referred to as BAFA) represented by the following formula

4-{[4-(1,3-dioxoisobenzofuran-5-ylcarbonyloxy)phenyl]cyclohexyl}phenyl 1,3-dioxoisobenzofuran-5-carboxylate (hereinafter, (Also referred to as BPZ-TME)

4-[4-(1,3-dioxoisobenzofuran-5-ylcarbonyloxy)-2,3,5-trimethylphenyl]-2,3,6-trimethylphenyl 1,3 represented by the following formula -Dioxoisobenzofuran-5-carboxylate (hereinafter also referred to as TMPBP-TME)

[Example 1]
First, 3.87 g (15.0 mmol) of BAP and 9.25 g (15.0 mmol) of BPZ-TME were placed in a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube. Thereafter, 30.62 g of γ-butyrolactone (hereinafter also referred to as GBL) was further added to the reaction vessel.
After bubbling nitrogen for 10 minutes, the temperature was raised to 60° C. while stirring, and the reaction was carried out for 1.5 hours. Thereafter, by further reacting at 180° C. for 3 hours, the bisaminophenol and the acid anhydride were polymerized to prepare a polymerization solution.
The obtained polymerization solution was diluted with acetone to prepare a diluted solution, and then the diluted solution was dropped into a mixed solution of water/methanol = 3/1 to precipitate a white solid. The obtained white solid was collected and vacuum-dried at a temperature of 120°C to obtain 8.17 g of polymer A represented by the following formula.
When polymer A was measured by GPC, the weight average molecular weight Mw was 45,400, the polydispersity (weight average molecular weight Mw/number average molecular weight Mn) was 2.04, and the average value of n of the polymer expressed by the following formula was 25. Met.

[Example 2]
First, 3.87 g (15.0 mmol) of BAP and 9.28 g (15.0 mmol) of TMPBP-TME were placed in a reaction vessel of an appropriate size equipped with a stirrer and a cooling tube. Thereafter, 30.69 g of GBL was further added to the reaction vessel.
After bubbling nitrogen for 10 minutes, the temperature was raised to 60° C. while stirring, and the reaction was carried out for 1.5 hours. Thereafter, by further reacting at 180° C. for 3 hours, the bisaminophenol and the acid anhydride were polymerized to prepare a polymerization solution.
The obtained polymerization solution was diluted with acetone to prepare a diluted solution, and then the diluted solution was dropped into a mixed solution of water/methanol = 3/1 to precipitate a white solid. The obtained white solid was collected and vacuum-dried at a temperature of 120°C to obtain 10.15 g of polymer.
When the polymer was measured by GPC, the weight average molecular weight Mw was 142,000, the polydispersity (weight average molecular weight Mw/number average molecular weight Mn) was 2.21, and the average value of n of polymer B expressed by the following formula was 73. Met.
When IR measurement was performed on Polymer B, the peaks derived from amide groups around 1480, 1550, and 1670 cm ⁻¹ disappeared, confirming that imidization was complete.

[Example 3]
First, 27.47 g (75.0 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter also referred to as BAFA) was placed in an appropriately sized reaction vessel equipped with a stirrer and a cooling tube. and 46.39 g (75.0 mmol) of TMPBP-TME were added. Then, an additional 295.46 g of GBL was added to the reaction vessel.
After bubbling nitrogen for 10 minutes, the temperature was raised to 60° C. while stirring, and the reaction was carried out for 1.5 hours. Thereafter, by further reacting at 180° C. for 3 hours, the bisaminophenol and the acid anhydride were polymerized to prepare a polymerization solution.
The obtained polymerization solution was diluted with acetone to prepare a diluted solution, and then the diluted solution was dropped into a mixed solution of water/methanol = 3/1 to precipitate a white solid. The obtained white solid was collected and vacuum-dried at a temperature of 120°C to obtain 66.62 g of Polymer C.
When the polymer was measured by GPC, the weight average molecular weight Mw was 87,200, the polydispersity (weight average molecular weight Mw / number average molecular weight Mn) was 1.92, and the average value of n of the polymer expressed by the following formula was 46. there were.
When IR measurement was performed on Polymer C, the peaks derived from amide groups around 1480, 1550, and 1670 cm ⁻¹ disappeared, confirming that imidization was complete.
Further, when ¹ H-NMR measurement was performed, a peak was confirmed in the aromatic region (6.9 ppm to 8.8 ppm) at an area ratio corresponding to the number of protons.

<Measurement method>
(Solubility of polyhydroxyimide in organic solvent)
The solubility of the polyhydroxyimides obtained in Examples 1 to 3 in γ-butyllactone (GBL) and OK73 (mixed solution of propylene glycol monomethyl ether acetate: 7/propylene glycol monomethyl ether: 3) was evaluated based on the following criteria. did. The results are shown in Table 1.
(Solubility evaluation criteria)
○: Polymer dissolved at 5% by mass or more △: Polymer dissolved at 1 to 5% by mass ×: Polymer dissolved at less than 1% by mass (dissolution rate of polyhydroxyimide in organic solvent)

Further, the dissolution rate for cyclopentanone was confirmed by the following method.
A 12% by mass GBL solution (polymer solution) of the polymers of Examples 1 to 3 was prepared and spin-coated onto the surface of a silicon wafer. Then, GBL was dried by prebaking at 120° C. for 3 minutes. A resin film was formed in the above manner.
The dissolution rate of this resin film in cyclopentanone was measured at a temperature of 23°C. The dissolution rate was calculated from the initial thickness of the resin film and the time required for the resin film to completely dissolve when the resin film was immersed in cyclopentanone.
The results are shown in Table 1.

(5% weight loss temperature (Td5))
A film was prepared by spin-coating a 12% by mass GBL solution (polymer solution) of the polymers of Examples 1 to 3 on the silicon wafer surface, pre-baking at 120°C for 3 minutes, and post-baking at 170°C for 120 minutes under nitrogen. did.
It was measured by simultaneous thermogravimetric differential thermal measurement. The measurement conditions were a nitrogen flow of 30 ml/min and a temperature increase rate of 10° C./min. The temperature at which the weight decreased by 5% from the initial stage was measured and defined as the 5% weight loss temperature (Td5). The results are shown in Table 1.

(Coefficient of linear thermal expansion (CTE))
A strip-shaped test piece with a length of 13 mm and a width of 5 mm was cut from a film obtained in the same manner as described in "5% Weight Loss Temperature (Td5)". Thermomechanical measurement in tensile mode was performed with a distance between chucks of 10 mm, and the average coefficient of linear thermal expansion (CTE, 50° C. to 200° C.) was determined from the thermal expansion curve. The results are shown in Table 1.

(Glass transition temperature: Tg)
A strip-shaped test piece with a length of 50 mm and a width of 5 mm was cut from a film obtained in the same manner as described in "5% Weight Loss Temperature (Td5)". Dynamic viscoelasticity was measured with a distance between chucks of 20 mm, and the peak temperature of the resulting loss tangent (tan δ) was defined as the glass transition temperature (Tg). The measurement conditions were a nitrogen flow of 30 ml/min, an applied frequency of 0.1 Hz, and a rate of 5° C./min. The results are shown in Table 1.

(Tensile strength, elongation and elastic modulus)
A test piece (6.5 mm x 60 mm x 10 μm thick) obtained by curing a polyhydroxyimide solution (polymer solution) at 170°C for 120 minutes in a nitrogen atmosphere was subjected to a tensile test (stretching speed: 5 mm). /min) in a 23°C atmosphere. The tensile test was conducted using a tensile tester (Tensilon RTC-1210A) manufactured by Orientech. Five test pieces were measured, and the stress at the breaking point was averaged to determine the strength. The tensile elongation rate was calculated from the fracture distance and the initial distance, and the maximum value and average value of the elongation rate were determined. The tensile modulus of elasticity was calculated from the initial slope of the obtained stress-strain curve, and the averaged value was taken as the modulus of elasticity. The results are shown in Table 1.
Note that a strain-stress curve for the film obtained using the polymer solution of Example 3 is shown in FIG. The strain-stress curve shows that before the yield point, strength is improved due to elongation due to deformation of the polymer main chain, and after the yield point, strong packing between polymer chains suppresses breakage due to polymer chains slipping through. It is thought that the strength was improved due to the increased elongation and excellent flexibility.

From the results in Table 1, the polyhydroxyimide of the present invention has excellent solubility in solvents and does not need to be made into a varnish in the precursor state, so that a resin film with excellent dimensional stability can be obtained. became clear. Furthermore, it has been revealed that a resin film with excellent mechanical strength can be obtained using the polyhydroxyimide of the present invention.

[Example 4]
(Preparation of photosensitive resin composition)
The polymer solution of Example 3 (100 parts by mass of polymer), tetramethoxymethylglycoluril (50 parts by mass) as a crosslinking agent, and di(trifluoromethanesulfone)imide (4,8-di-n-butoxy-) as a photosensitizer. A photosensitive resin composition was prepared by mixing 1-naphthyl)dibutylsulfonium (3 parts by mass) and FC4432 (0.05 parts by mass) as a surfactant.

(Evaluation regarding patterning characteristics)
It was confirmed as follows that the photosensitive resin composition of Example 4 could be sufficiently patterned by exposure and development.
The photosensitive resin composition of Example 4 was applied onto an 8-inch silicon wafer using a spin coater. After coating, it was prebaked for 3 minutes at 120° C. on a hot plate in the atmosphere to obtain a coating film with a thickness of about 5.0 μm.
This coating film was irradiated with i-line through a mask on which a via pattern with a width of 20 μm was drawn. For irradiation, an i-line stepper (NSR-4425i, manufactured by Nikon Corporation) was used.
After exposure, the wafer was placed on a hot plate and baked at 120° C. for 5 minutes in the atmosphere.
Thereafter, spray development was carried out for 20 seconds using cyclopentanone as a developer, and further spray development was carried out for 10 seconds using PGMEA as a developer to dissolve and remove the unexposed areas to obtain a via pattern.
The cross section of the obtained via pattern was observed using a desktop SEM. The width at the middle height between the bottom surface of the via pattern and the opening was defined as the via width, and evaluation was made based on the following criteria.
Good patterning properties: 20 μm via pattern opens. Poor patterning properties: 20 μm via pattern does not open. The patterning properties of Example 4 were good.

Claims (7)

A polyhydroxyimide having a repeating structure represented by the following general formula (1).

(In the general formula (1), X represents -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -, and multiple Xs may be the same or different. ) and a group represented by the following general formula (1b), and a plurality of Y's may be the same or different. n is a number of 2 to 500 as an average value.)

(In the general formula (1a), R ¹ , R ² and R ³ represent a hydrogen atom. In the general formula (1b), R ⁴ and R ⁵ each independently represent a hydrogen atom or a hydrogen atom having 1 to 3 carbon atoms. Indicates an alkyl group, at least one of R ⁴ and at least one of R ⁵ is an alkyl group having 1 to 3 carbon atoms, and a plurality of R ^4s and a plurality of R ^5s may be the same or different. Good. * indicates a bond.) A polymer solution comprising the polyhydroxyimide according to claim 1 and an organic solvent. A photosensitive resin composition comprising a polyhydroxyimide having a repeating structure represented by the following general formula (1) , a crosslinking agent, and a photosensitizer.

(In general formula (1), X is a single bond, -SO ₂ -, -C(=O)-, a linear or branched alkylene group having 1 to 5 carbon atoms, or a linear or It represents a branched fluoroalkylene group, and multiple X's may be the same or different.Y is selected from the groups represented by the following general formula (1a) and the following general formula (1b), and the multiple Y's are They may be the same or different. n is an average value of 2 to 500.)

(In general formula (1a), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a plurality of R ^1s exist , A plurality of R ^2s may be the same or different. R ³ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbons, and a plurality of R ^3s may be the same. In the general formula (1b), R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and Existing R ^4s and multiple R ^5s may be the same or different. * indicates a bond.) A cured film comprising a cured product of the photosensitive resin composition according to claim 3 . A semiconductor device comprising a resin film containing a cured product of the photosensitive resin composition according to claim 3 . an interlayer insulating film;
A resin film comprising a cured product of the photosensitive resin composition according to claim 3 , provided on the interlayer insulating film;
rewiring embedded in the resin film;
6. The semiconductor device according to claim 5 , comprising: A general formula comprising a step of imidizing a bisaminophenol represented by the following general formula (a) and an acid anhydride represented by the following general formula (b) at a temperature of 100 ° C. or more and 250 ° C. or less A method for producing polyhydroxyimide having a repeating structure represented by (1).

(In general formula (a), X represents -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ - .)

(In the general formula (b), Y is selected from the groups represented by the following general formulas (1a) and (1b).)

(In the general formula (1a), R ¹ , R ² and R ³ represent a hydrogen atom. In the general formula (1b), R ⁴ and R ⁵ each independently represent a hydrogen atom or a hydrogen atom having 1 to 3 carbon atoms. Indicates an alkyl group, at least one of R ⁴ and at least one of R ⁵ is an alkyl group having 1 to 3 carbon atoms, and a plurality of R ^4s and a plurality of R ^5s may be the same or different. Good. * indicates a bond.)

(In general formula (1), X has the same meaning as general formula (a), and Y has the same meaning as general formula (b). n is a number from 2 to 500 as an average value.)

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