JP2024033021A - Metal removing method using metal removing filter for removing metal impurity in photosensitive resin composition - Google Patents

Abstract

To provide a purification material composition which has no denaturation of polyamic acid ester, removes metal impurities in a photosensitive resin composition used in a packaging step in manufacture of a semiconductor device while maintaining high viscosity of the photosensitive resin composition, and is highly purified.SOLUTION: A metal removing method removes metal impurity in a photosensitive resin composition by filtration using a metal removing filter having a porous membrane which has an ultrahigh molecular weight and is made of polyethylene, and a resin layer arranged so as to cover at least a part of the porous membrane.SELECTED DRAWING: None

Description

The present invention relates to a metal removal method using a metal removal filter for removing metal impurities in a photosensitive resin composition or a polyamic acid ester solution.

Many chemicals are used in the manufacture of semiconductor devices. For example, polyamic acid ester is used as a photosensitive insulating film used in the packaging process during semiconductor device manufacturing. If metal ions or chargeable colloidal substances derived from metals or metal oxides remain in this polyamic acid ester, unexpected adverse effects may occur on the final product or during its manufacturing process.

The above-mentioned metal impurities may be impurities derived from raw materials, residual metal catalysts used in organic reactions, or impurities derived from reaction vessels used during polymer synthesis.
Generally, most of the alkali metals and alkaline earth metals can be removed using ion exchange resins. However, polyvalent metal ions and chargeable metal oxide colloidal particles of these metals are difficult to adsorb and remove with ion exchange resins, and chelate resins are used for the purpose of removing them (Patent Document 1, (See Patent Document 2). On the other hand, metal ions and chargeable metal oxide colloidal particles have a wide variety of ionic strengths, ionic radii, and particle sizes, and chelate resins may not fit the morphology of the metal species depending on the type of functional group, and may not be able to hold enough metal. It may not exhibit adsorption ability, and it is necessary to use a combination of chelate resins in order to remove several types of metal impurities in the target resin.

International publication pamphlet WO2015-146307 publication Special Publication No. 2008-502470

To remove metal impurities, it is common to use a cationic ion exchange resin containing a sulfo group and having a microporous carrier made of a copolymer of styrene and divinylbenzene. However, metal removal methods using sulfo group-containing cationic ion-exchange resins can cause polyamic acid esters to be modified if they are used as photosensitive insulating films used in the packaging process during semiconductor device manufacturing. Therefore, it is not desirable. On the other hand, in order to remove metals without denaturing the polyamic acid ester solution, there is a metal removal method using chelate resin treatment. It must be treated in a dilute solution state. The thickness of the photosensitive insulating film used in the packaging process during the manufacture of semiconductor devices is as thick as about several tens of micrometers, and the solid content concentration is relatively high, resulting in high viscosity. For this reason, in metal removal treatment using chelate resin, it is difficult to effectively bring the chelate resin into contact with the photosensitive insulating film composition, and metal removal treatment using chelate resin is not suitable for the above applications. .

The present invention removes metal impurities in a photosensitive resin composition used in the packaging process during semiconductor device manufacturing from a composition in which the material to be purified is dissolved by filtering it using a specific metal removal filter, The purpose is to obtain a highly purified purified material composition (also referred to as a purified photosensitive resin composition).
Furthermore, the present invention aims to obtain a highly purified purified organic solution (which can also be called a purified organic solution) by filtering metal impurities in a normal organic solution using a specific metal removal filter. be.

［式中、Ｘ^１は、４価の有機基であり、Ｙ^１は、２価の有機基であり、Ｒ^１及びＲ^２は、それぞれ独立に、１価の有機基である。］
第３観点として、前記感光性樹脂組成物が有機溶剤を含有する溶液である第１観点または第２観点に記載の金属除去方法に関する。
第４観点として、前記金属除去フィルターを用いたろ過により除去する金属不純物が国際純正応用化学連合（ＩＵＰＡＣ：Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｕｎｉｏｎ ｏｆ Ｐｕｒｅ ａｎｄ Ａｐｐｌｉｅｄ Ｃｈｅｍｉｓｔｒｙ）が定めた表示法に従う周期表の第２周期乃至第６周期で第１族乃至第１４族の金属、その多価金属イオン、又はそれらの金属水酸化物若しくは金属酸化物のコロイド物質である、第１観点乃至第３観点のいずれか一つに記載の金属除去方法に関する。
第５観点として、下記一般式（１）からなる構造単位を有する化合物を含む有機溶液中の金属不純物を、超高分子量ポリエチレン製の多孔性膜と、該多孔性膜の少なくとも一部を覆うように配置された樹脂層とを有する金属除去フィルターを用いた濾過により除去する金属除去方法に関する、

［式中、Ｘ^１は、４価の有機基であり、Ｙ^１は、２価の有機基であり、Ｒ^１及びＲ^２は、それぞれ独立に、１価の有機基である。］
第６観点として、前記金属除去フィルターを用いたろ過により除去する金属不純物が国際純正応用化学連合（ＩＵＰＡＣ：Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｕｎｉｏｎ ｏｆ Ｐ
ｕｒｅ ａｎｄ Ａｐｐｌｉｅｄ Ｃｈｅｍｉｓｔｒｙ）が定めた表示法に従う周期表の第２周期乃至第６周期で第１族乃至第１４族の金属、その多価金属イオン、又はそれらの金属水酸化物若しくは金属酸化物のコロイド物質である、第５観点に記載の金属除去方法に関する。
第７観点として、前記第１観点乃至第４観点に記載される金属除去方法を用いて得られた感光性樹脂組成物中に、国際純正応用化学連合（ＩＵＰＡＣ：Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｕｎｉｏｎ ｏｆ Ｐｕｒｅ ａｎｄ Ａｐｐｌｉｅｄ Ｃｈｅｍｉｓｔｒｙ）が定めた表示法に従う第２周期乃至第６周期で第１族乃至第１４族の金属、その多価金属イオン、又はそれらの金属水酸化物若しくは金属酸化物のコロイド物質が１００乃至１０００ｐｐｔ含まれる、精製された感光性樹脂組成物に関する。
第８観点として、前記第５観点または第６観点に記載される金属除去方法を用いて得られた有機溶液中に、国際純正応用化学連合（ＩＵＰＡＣ：Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｕｎｉｏｎ ｏｆ Ｐｕｒｅ ａｎｄ Ａｐｐｌｉｅｄ Ｃｈｅｍｉｓｔｒｙ）が定めた表示法に従う第２周期乃至第６周期で第１族乃至第１４族の金属、その多価金属イオン、又はそれらの金属水酸化物若しくは金属酸化物のコロイド物質が１００乃至１０００ｐｐｔ含まれる、精製された有機溶液に関する。 As a first aspect, the present invention eliminates metal impurities in a photosensitive resin composition by using a porous membrane made of ultra-high molecular weight polyethylene and a resin layer disposed to cover at least a portion of the porous membrane. Regarding a method for removing metals by filtration using a metal removal filter,
As a second aspect, the photosensitive resin composition is characterized in that it contains a polyamic acid ester, and the polyamic acid ester is a compound having a structural unit consisting of the following general formula (1). Relating to a metal removal method.

[In the formula, X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and R ¹ and R ² are each independently a monovalent organic group. ]
A third aspect relates to the metal removal method according to the first or second aspect, wherein the photosensitive resin composition is a solution containing an organic solvent.
A fourth aspect is that the metal impurities removed by filtration using the metal removal filter are in periods 2 to 6 of the periodic table according to the notation method established by the International Union of Pure and Applied Chemistry (IUPAC). According to any one of the first to third aspects, the material is a colloidal material of a metal of Group 1 to Group 14, a polyvalent metal ion thereof, or a metal hydroxide or metal oxide thereof. Relating to a metal removal method.
As a fifth aspect, metal impurities in an organic solution containing a compound having a structural unit represented by the following general formula (1) are removed using a porous membrane made of ultra-high molecular weight polyethylene and a method that covers at least a portion of the porous membrane. A method for removing metals by filtration using a metal removal filter having a resin layer arranged on the

[In the formula, X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and R ¹ and R ² are each independently a monovalent organic group. ]
As a sixth aspect, the metal impurities removed by filtration using the metal removal filter are classified by the International Union of Pure and Applied Chemistry (IUPAC).
Metals of Groups 1 to 14 in Periods 2 to 6 of the periodic table, their polyvalent metal ions, or their metal hydroxides or metal oxides The present invention relates to a method for removing a metal according to the fifth aspect, which is a colloidal substance.
As a seventh aspect, in the photosensitive resin composition obtained using the metal removal method described in the first to fourth aspects, International Union of Pure and Applied Chemistry (IUPAC) is present. 100 to 1000 ppt of colloidal substances of Group 1 to Group 14 metals, their polyvalent metal ions, or their metal hydroxides or metal oxides are included in the second to sixth periods according to the display method specified by , relates to a purified photosensitive resin composition.
As an eighth aspect, in the organic solution obtained using the metal removal method described in the fifth aspect or the sixth aspect, the metals specified by the International Union of Pure and Applied Chemistry (IUPAC) are present. Refined products containing 100 to 1000 ppt of colloidal substances of Group 1 to Group 14 metals, their polyvalent metal ions, or their metal hydroxides or metal oxides in the second to sixth periods according to the notation method. related to organic solutions.

The present invention provides a metal removal method for removing metal impurities in a photosensitive resin composition solution using a metal removal filter.
The present invention uses a specific metal removal filter to filter out metal impurities in the photosensitive resin composition used in the packaging process during semiconductor device manufacturing, so that the photosensitive resin composition can be removed without modification of the polyamic acid ester. It has become possible to effectively obtain highly purified and purified material compositions while maintaining high viscosity.

The present invention is a metal removal method for removing metal impurities in a solution using a metal removal filter, and the solution is a photosensitive resin composition solution mainly containing a polyamic acid ester. The photosensitive resin composition used as a component of the solution to be purified of the present invention includes (A) a polyamic acid ester, optionally (B) a carboxylic acid compound or anhydride thereof, (C) an isocyanate compound, and (P) the above polyamic acid ester. Consists of polymer compounds other than (A) and other components.

[(A) Polyamic acid ester]
Polyamic acid ester is a resin component contained in a photosensitive resin composition, and has a unit structure represented by the following general formula (1).

［式中、Ｘ^１は、４価の有機基であり、Ｙ^１は、２価の有機基であり、Ｒ^１及びＲ^２は、それぞれ独立に、１価の有機基である。］

[In the formula, X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and R ¹ and R ² are each independently a monovalent organic group. ]

In the above general formula (1), X ¹ is not particularly limited as long as it is a tetravalent organic group, but from the viewpoint of achieving both heat resistance and photosensitivity, it is preferably a tetravalent organic group having 6 to 40 carbon atoms. More preferably, it is an aromatic group in which the -COOR ¹ group, the -COOR ² group, and the -CONH- group are in ortho positions, or an alicyclic aliphatic group. Further, the tetravalent organic group represented by X ¹ is more preferably an organic group containing an aromatic ring and having 6 to 40 carbon atoms.

More preferably, X ¹ is a tetravalent organic group represented by the following formula (5) or the following formulas (5-1) to (5-7).

Moreover, the structure of X ¹ may be one type or a combination of two or more types.

In the above general formula (1), Y ¹ is not limited as long as it is a divalent organic group having 6 to 40 carbon atoms, but may be substituted from the viewpoint of achieving both heat resistance and photosensitivity. It is preferably a cyclic organic group having 1 to 4 aromatic or aliphatic rings, or an aliphatic group or siloxane group having no cyclic structure. More preferably, Y ¹ has a structure represented by the following general formula (6), the following general formula (7), or the following formula (8).

(In the formula, A each independently represents a methyl group (-CH ₃ ), an ethyl group (-C ₂ H ₅ ), a propyl group (-C ₃ H ₇ ), or a butyl group (-C ₄ H ₉ ) .}

Moreover, the structure of Y ¹ may be one type or a combination of two or more types.

In the above general formula (1), R ¹ and R ² are not particularly limited as long as they are each independently a monovalent organic group. For example, R ¹ and R ² each independently represent a monovalent aliphatic group having 1 to 30 carbon atoms, or 5 to 22 carbon atoms, a cycloaliphatic group, or a bond between an aromatic group and an aliphatic group. or a group in which these groups are substituted with a halogen atom, a nitro group, an amino group, a cyano group, a methoxy group, an acetoxy group, or the like. Typical halogen atoms are F, Cl, Br, and I.

Preferably, R ¹ and R ² each independently represent the following general formula (2):

(In the formula, R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, and m is an integer of 1 to 10. * is , is the bonding site with the carboxylic acid present in the polyamic acid main chain of general formula (1).)
It is preferable that it is expressed as

R ¹ and R ² each independently represent the following general formula (3):

(In the formula, R ⁶ is a monovalent group selected from alkyl groups having 1 to 30 carbon atoms. * is the same as above.)
A monovalent organic group represented by may be included.

R ¹ and R ² in the above general formula (1) may each be one type or a combination of two or more types, but preferably a combination of three or less types, preferably a combination of two types, and most preferably one type. It is a seed.

In the above general formula (1), from the viewpoint of the photosensitive properties and mechanical properties of the photosensitive resin composition, the monovalent organic group represented by the above general formula (2) for all of R ¹ and R ² and the above general formula The total proportion of monovalent organic groups represented by (3) is preferably 80 mol% or more, preferably 90 mol% or more, and preferably 100 mol%.

In the above general formula (1), from the viewpoint of the photosensitive properties and mechanical properties of the photosensitive resin composition, the total ratio of monovalent organic groups represented by the above general formula (2) to all of R ¹ and R ² is preferably 80 mol% or more, preferably 90 mol% or more, and preferably 100 mol%.

R ³ in the above general formula (2) is not limited as long as it is a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms; It is preferable that it is a group.

R ⁴ and R ⁵ in the above general formula (2) are not limited as long as they are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, but may affect the photosensitive properties of the photosensitive resin composition. From this point of view, a hydrogen atom is preferable.

m in the above general formula (2) is an integer of 1 or more and 10 or less, and preferably an integer of 2 or more and 4 or less from the viewpoint of photosensitive characteristics.

R ⁶ in the above general formula (3) is not limited as long as it is a monovalent organic group selected from alkyl groups having 1 to 30 carbon atoms. An alkyl group having 5 to 30 carbon atoms is preferred, an alkyl group having 8 to 30 carbon atoms is preferred, an alkyl group having 9 to 30 carbon atoms is preferred, an alkyl group having 10 to 30 carbon atoms is preferred. Preferably, an alkyl group having 11 to 30 carbon atoms is more preferable, and an alkyl group having 17 to 30 carbon atoms is even more preferable. It may have not only a linear structure but also a branched structure and a cyclic structure.

Specifically, R ⁶ is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group (amyl group), a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group ( lauryl group), tridecyl group, tetradecyl group (myristyl group), pentadecyl group, hexadecyl group (palmityl group), heptadecyl group (margaryl group), octadecyl group (stearyl group), nonadecyl group, icosyl group (arakyl group), henicosyl group , linear alkyl groups such as docosyl group (behenyl group), tricosyl group, tetracosyl group (lignoceryl group), pentacosyl group, hexacosyl group, heptacosyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, Isopentyl group, neopentyl group, tert-pentyl group, sec-isoamyl group, isohexyl group, neohexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group , 4-ethylhexyl group, 2-ethylpentyl group, heptane-3-yl group, heptane-4-yl group, 4-methylhexan-2-yl group, 3-methylhexan-3-yl group, 2,3- Dimethylpentan-2-yl group, 2,4-dimethylpentan-2-yl group, 4,4-dimethylpentan-2-yl group, 6-methylheptyl group, 2-ethylhexyl group, octan-2-yl group, 6-methylheptan-2-yl group, 6-methyloctyl group, 3,5,5-trimethylhexyl group, nonan-4-yl group, 2,6-dimethylheptan-3-yl group, 3,6-dimethyl Heptane-3-yl group, 3-ethylheptan-3-yl group, 3,7-dimethyloctyl group, 8-methylnonyl group, 3-methylnonan-3-yl group, 4-ethyloctan-4-yl group, 9 -Methyldecyl group, undecane-5-yl group, 3-ethylnonan-3-yl group, 5-ethylnonan-5-yl group, 2,2,4,5,5-pentamethylhexan-4-yl group, 10- Methylundecyl group, 11-methyldodecyl group, tridecane-6-yl group, tridecane-7-yl group, 7-ethylundecane-2-yl group, 3-ethylundecane-3-yl group, 5-ethylundecane-yl group 5-yl group, 12-methyltridecyl group, 13-methyltetradecyl group, pentadecane-7-yl group, pentadecane-8-yl group, 14-methylpentadecyl group, 15-methylhexadecyl group, heptadecan-8 -yl group, heptadecan-9-yl group, 3,13-dimethylpentadecane-7-yl group, 2,2,4,8,10,10-hexamethylundecane-5-yl group, 16-methylheptadecyl group , 17-methyloctadecyl group, nonadecan-9-yl group, nonadecan-10-yl group, 2,6,10,14-tetramethylpentadecane-7-yl group, 18-methylnonadecyl group, 19-methylicosyl group, henicosane- 10-yl group, 20-methylhenicosyl group, 21-methyldocosyl group, tricosan-11-yl group, 22-methyltricosyl group, 23-methyltetracosyl group, pentacosan-12-yl group, pentacosan-13 -yl group, 2,22-dimethyltricosan-11-yl group, 3,21-dimethyltricosan-11-yl group, 9,15-dimethyltricosan-11-yl group, 24-methylpentacosyl group , 25-methylhexacosyl group, heptacosan-13-yl group; branched alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-tert-butylcyclohexyl group, 1,6- Dimethylcyclohexyl group, menthyl group, cycloheptyl group, cyclooctyl group, bicyclo[2.2.1]heptan-2-yl group, bornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, tricyclo[5. Examples thereof include alicyclic alkyl groups such as a tricyclo[5.2.1.02,6]decane-4-yl group, a tricyclo[5.2.1.02,6]decane-8-yl group, and a cyclododecyl group.

Preferably, R ⁶ is the following formula (4):

(Z ¹ is hydrogen or an alkyl group having 1 to 14 carbon atoms,
Z ² is an alkyl group having 1 to 14 carbon atoms,
Z ³ is an alkyl group having 1 to 14 carbon atoms,
However, Z ¹ , Z ² and Z ³ may be the same or different,
The total number of carbon atoms of Z ¹ , Z ² and Z ³ is 4 or more. ) is preferably represented.

Preferably Z ¹ is hydrogen.
Z ¹ , Z ² and Z ³ are preferably alkyl groups having 2 to 12 carbon atoms, more preferably alkyl groups having 2 to 10 carbon atoms.
The total number of carbon atoms of Z ¹ , Z ² and Z ³ is preferably 5 or more, preferably 6 or more, preferably 10 or more, preferably 12 or more, and 14 or more. The number is preferably 15 or more, and preferably 16 or more.
The total number of carbon atoms of Z ¹ , Z ² and Z ³ is preferably 6 or more and 20 or less.
The upper limit of the total number of carbon atoms in Z ¹ , Z ² and Z ³ is preferably 28.

Further, R ⁶ may be selected from the following formulas (3-1) to (3-7).

The R ⁶ is preferably selected from the above formulas (3-1) to (3-7).

[Method for preparing polyamic acid ester]
The polyamic acid ester represented by the above general formula (1) in this embodiment includes, for example, the above-mentioned tetracarboxylic dianhydride containing the tetravalent organic group X ¹ having 6 to 40 carbon atoms; Alcohols formed by bonding a monovalent organic group represented by general formula (2) and a hydroxyl group, and (b) alcohols formed by bonding a monovalent organic group represented by general formula (3) above and a hydroxyl group. A partially esterified tetracarboxylic acid (hereinafter also referred to as acid/ester) is prepared by reacting an alcohol ^consisting of It can be obtained by polycondensation with diamines containing.

(Preparation of acid/ester form)
In this embodiment, examples of the tetracarboxylic dianhydride containing a tetravalent organic group ^X1 having 6 to 40 carbon atoms include pyromellitic anhydride, diphenyl ether-3,3',4,4'-tetracarboxylic acid Acid dianhydride (=4,4'-oxydiphthalic dianhydride), benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetra Carboxylic dianhydride, diphenylsulfone-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis Examples include (3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, and the like.

Further, tetracarboxylic dianhydrides represented by the following formulas (5-1-a) to (5-7-a) are also exemplified.

These can be used alone or in a mixture of two or more.

In this embodiment, (a) alcohols having a structure represented by the above general formula (2) include, for example, 2-acryloyloxyethyl alcohol, 1-acryloyloxy-3-propyl alcohol, methylol vinyl ketone, -Hydroxyethyl vinyl ketone, 2-hydroxy-3-methoxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-methacryloyloxyethyl alcohol, 1-methacryloyloxy-3-propyl alcohol, 2-hydroxy-3-methoxy Examples include propyl methacrylate, 2-hydroxy-3-butoxypropyl methacrylate, and 2-hydroxyethyl methacrylate.

(b) As the aliphatic alcohol having 1 to 30 carbon atoms having the structure represented by the above general formula (3), for example, the hydrogen atom of the above alkyl group having 1 to 30 carbon atoms has been substituted with a hydroxy group. Examples include alcohols.

Also, alcohols having the structures of the above formulas (3-1) to (3-6) may be used. The following commercial products may be used.
Alcohols containing the structure of formula (3-1): Fine Oxocol (registered trademark) 180 (manufactured by Nissan Chemical Co., Ltd.),
Alcohols containing the structure of formula (3-2): Fine Oxokol (registered trademark) 2000 (manufactured by Nissan Chemical Co., Ltd.),
Alcohols containing the structure of formula (3-3): Fine Oxocol (registered trademark) 180N (manufactured by Nissan Chemical Co., Ltd.),
Alcohols containing the structure of formula (3-4) or formula (3-5): Fine Oxokol (registered trademark) 180T (manufactured by Nissan Chemical Co., Ltd.),
Alcohol containing the structure of formula (3-6): Fine Oxocol (registered trademark) 1600K (manufactured by Nissan Chemical Co., Ltd.).
As these alcohols, it is preferable to use alcohols having the structures of the above formulas (3-1) to (3-6).

The total content of the components (a) and (b) in the photosensitive resin composition is preferably 80 mol% or more based on the total content of R ¹ and R ² in the general formula (1). In order to obtain a low dielectric constant and a low dielectric loss tangent, the content of component (b) is preferably 1 mol % to 90 mol % with respect to the total content of R ¹ and R ² .

The above tetracarboxylic dianhydride and the above alcohol are stirred, dissolved, and mixed in a reaction solvent at a reaction temperature of 0 to 100°C for 10 to 40 hours in the presence of a basic catalyst such as pyridine. As a result, the half-esterification reaction of the acid dianhydride progresses, and the desired acid/ester compound can be obtained.

The reaction solvent is preferably one that dissolves the acid/ester and the polyamic acid ester, which is a polycondensation product of the acid/ester and diamines, such as N-methyl-2-pyrrolidone, N-methyl-2-pyrrolidone, -Ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea, gamma-butyrolactone, ketones, esters, lactones, ethers, halogenated hydrocarbons, carbonized Hydrogens, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4 -dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene and the like. These may be used alone or in combination of two or more, if necessary.

(Preparation of polyamic acid ester)
A known dehydration condensation agent such as dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, Add and mix 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, N,N'-diisopropylcarbodiimide, etc. to convert the acid/ester form into polyacid. After forming the anhydride, diamines containing a divalent organic group Y ¹ having 6 to 40 carbon atoms are separately dissolved or dispersed in a solvent and added dropwise thereto, followed by polycondensation. It is possible to obtain a polyamic acid ester that can be used in

Examples of diamines containing a divalent organic group Y ¹ having 6 to 40 carbon atoms include p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3 '-Diamino diphenyl ether, 4,4'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3 , 3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis( 4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4, 4'-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl] ] Ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4- aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-amino) phenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, ortho-toridine sulfone, 9,9-bis(4-aminophenyl)fluorene, and hydrogen atoms on their benzene rings partially substituted with a methyl group, ethyl group, hydroxymethyl group, hydroxyethyl group, halogen atom, etc., such as 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl -4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethitoxy-4,4' -diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, and mixtures thereof.
Also included are diamines represented by the following formula (8-1).

The diamines used in this application are not limited to these.

In the embodiment, in order to improve the adhesion between the photosensitive resin layer formed on the substrate by coating the photosensitive resin composition on the substrate and various substrates, 1 is added at the time of preparing the polyamic acid ester. , 3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(3-aminopropyl)tetraphenyldisiloxane, and other diaminosiloxanes can also be copolymerized.

After the completion of the polycondensation reaction, the water-absorbed by-products of the dehydration condensation agent coexisting in the reaction solution are filtered off as necessary, and then a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof is removed. , the polymer component is precipitated by adding it to the reaction solution, and the polymer is purified by repeating re-dissolution, reprecipitation, etc., and vacuum-dried to obtain a polyamic acid that can be used in the embodiment. Isolate the ester.

The molecular weight of the polyamic acid ester is preferably from 5,000 to 150,000, more preferably from 7,000 to 50,000, when measured as a polystyrene equivalent weight average molecular weight by gel permeation chromatography. . When the weight average molecular weight is 5,000 or more, it is preferable because the mechanical properties are good, while when it is 150,000 or less, the dispersibility in the developer and the resolution performance of the relief pattern are poor. It is preferable because it is good.

[(B) Carboxylic acid compound or its anhydride]
The photosensitive resin composition of the present invention contains (B) a carboxylic acid compound represented by the following general formula (30) or its anhydride.

［式中、Ｚ^４及びＺ^５は、それぞれ独立に、
水素原子、ハロゲン原子、ヒドロキシ基、メルカプト基、カルボキシ基、シアノ基、ホルミル基、ハロホルミル基、スルホ基、ニトロ基、ニトロソ基、オキソ基、チオキシ基、
置換されていてもよい炭素原子数１～１０のアルキル基、アルコキシ基、もしくはアルキルスルファニル基、
置換されていてもよい炭素原子数２～１０のアルケニル基、アルキニル基、もしくはアルコキシカルボニル基、又は
置換されていてもよいアミノ基、イミノ基、もしくはカルバモイル基を表し、
Ｚ^４及びＺ^５は、相互に結合して、ヘテロ原子を含んでもよく、置換基を有していてもよく、縮合していてもよい環を形成してもよく、当該環が芳香族環であるとき、

はＨＯＯＣがＣＯＯＨに対してオルト位にある共役二重結合を示し、当該環が芳香族環であるとき以外の場合、

はＨＯＯＣとＣＯＯＨについてのシス型二重結合を示す。］

[In the formula, Z ⁴ and Z ⁵ are each independently,
Hydrogen atom, halogen atom, hydroxy group, mercapto group, carboxy group, cyano group, formyl group, haloformyl group, sulfo group, nitro group, nitroso group, oxo group, thioxy group,
an optionally substituted alkyl group having 1 to 10 carbon atoms, an alkoxy group, or an alkylsulfanyl group,
represents an optionally substituted alkenyl group, alkynyl group, or alkoxycarbonyl group having 2 to 10 carbon atoms, or an optionally substituted amino group, imino group, or carbamoyl group,
Z ⁴ and Z ⁵ may be bonded to each other to form a ring that may contain a hetero atom, may have a substituent, or may be fused, and the ring may be an aromatic ring. When

indicates a conjugated double bond in which HOOC is at the ortho position to COOH, unless the ring is an aromatic ring,

indicates the cis-type double bond for HOOC and COOH. ]

Preferably, the carboxylic acid compound or its anhydride (B) is a carboxylic acid compound or its anhydride represented by the following general formula (31).

［式中、Ｒ^３３～Ｒ^３６は、それぞれ独立に、
水素原子、ハロゲン原子、ヒドロキシ基、メルカプト基、カルボキシ基、シアノ基、ホルミル基、ハロホルミル基、
スルホ基、ニトロ基、ニトロソ基、オキソ基、チオキシ基、
置換されていてもよい炭素原子数１～６のアルキル基、アルコキシ基、もしくはアルキルスルファニル基、
置換されていてもよい炭素原子数２～６のアルケニル基、アルキニル基、もしくはアルコキシカルボニル基、又は
置換されていてもよいアミノ基、イミノ基、もしくはカルバモイル基を表し、
Ｒ^３３とＲ^３４、Ｒ^３４とＲ^３５、もしくはＲ^３５とＲ^３６は、相互に結合して、ヘテロ原子を含んでもよく、置換基を有していてもよく、縮合していてもよい環を形成してもよい。］

[In the formula, R ³³ to R ³⁶ are each independently,
Hydrogen atom, halogen atom, hydroxy group, mercapto group, carboxy group, cyano group, formyl group, haloformyl group,
Sulfo group, nitro group, nitroso group, oxo group, thioxy group,
an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkoxy group, or an alkylsulfanyl group,
represents an optionally substituted alkenyl group, alkynyl group, or alkoxycarbonyl group having 2 to 6 carbon atoms, or an optionally substituted amino group, imino group, or carbamoyl group,
R ³³ and R ³⁴ , R ³⁴ and R ³⁵ , or R ³⁵ and R ³⁶ are bonded to each other to form a ring that may contain a hetero atom, may have a substituent, or may be fused. may be formed. ]

Examples of the alkyl group include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group (amyl group), hexyl group, heptyl group, octyl group, nonyl group, and decyl group. ; Isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, sec-isoamyl group, isohexyl group, neohexyl group, 4-methylhexyl group, 5-methyl Hexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 2-ethylpentyl group, heptane-3-yl group, heptane-4-yl group, 4-methylhexane-2- yl group, 3-methylhexan-3-yl group, 2,3-dimethylpentan-2-yl group, 2,4-dimethylpentan-2-yl group, 4,4-dimethylpentan-2-yl group, 6 -Methylheptyl group, 2-ethylhexyl group, octan-2-yl group, 6-methylheptan-2-yl group, 6-methyloctyl group, 3,5,5-trimethylhexyl group, nonan-4-yl group, 2,6-dimethylheptan-3-yl group, 3,6-dimethylheptan-3-yl group, 3-ethylheptan-3-yl group, 3,7-dimethyloctyl group, 8-methylnonyl group, 3-methylnonane -3-yl group, branched alkyl group such as 4-ethyloctan-4-yl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-tert-butylcyclohexyl group, 1,6- Dimethylcyclohexyl group, menthyl group, cycloheptyl group, cyclooctyl group, bicyclo[2.2.1]heptan-2-yl group, bornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, tricyclo[5. Examples thereof include alicyclic alkyl groups such as a tricyclo[5.2.1.02,6]decane-4-yl group and a tricyclo[5.2.1.02,6]decane-8-yl group.

Specific examples of the alkoxy group, alkylsulfanyl group, and alkoxycarbonyl group include groups in which -O-, -S-, and -COO- are bonded to the above alkyl group, respectively.

Specific examples of the alkenyl group include ethenyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3- Examples include pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 1-heptenyl group, 2-heptenyl group, 5-heptenyl group, 1-octenyl group, 3-octenyl group, and 5-octenyl group. .

Specific examples of the alkynyl group include acetylenyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentethyl group, 2-pentethyl group, 3- Examples include pentethyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 1-heptynyl group, 2-heptynyl group, 5-heptynyl group, 1-octynyl group, 3-octynyl group, and 5-octynyl group. .

Specific examples of the ring when Z ⁴ and Z ⁵ are bonded to each other to form a ring that may contain a hetero atom, may have a substituent, and may be fused, and R ³³ and When R ³⁴ , R ³⁴ and R ³⁵ , or R ³⁵ and R ³⁶ are bonded to each other to form a ring that may contain a hetero atom, may have a substituent, or may be fused; Specific examples of the ring include benzene, naphthalene, anthracene, pyrrole, furan, thiophene, pyrrolidine, tetrahydrofuran, tetrahydrothiophene, pyridine, piperidine, tetrahydropyran, tetrahydrothiopyran, imidazole, pyrazole, oxazole, thiazole, imidazoline, dioxane, Morpholine, thiazine, triazole, dioxolane, pyridazine, pyrimidine, pyrazine, indole, isoindole, benzimidazole, purine, benzotriazole, quinoline, isoquinoline, quinazoline, quinoxaline, cinnoline, pteridine, chromene, isochromene, acridine, xanthene, carbazole, etc. Can be mentioned.

Examples of the substituent include a halogen atom, a hydroxy group, a mercapto group, a carboxy group, a cyano group, a formyl group, a haloformyl group, a sulfo group, an amino group, a nitro group, a nitroso group, an oxo group, a thioxy group, and a carbon atom number of 1 Examples include an alkyl group or haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a haloalkoxy group.

Preferably, Z ⁴ and Z ⁵ in the general formula (30) are a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms.

Some suitable carboxylic acid compounds or their anhydrides (B) are as follows.

上に例示したカルボン酸化合物は、酸無水物であってもよい。

The carboxylic acid compound exemplified above may be an acid anhydride.

The amount of the carboxylic acid compound or its anhydride (B) in the photosensitive resin composition according to the present invention is usually 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of the polyamic acid ester (A). .

The carboxylic acid compound or its anhydride (B) is chemically bonded to the polyamic acid ester (A) and/or a polymer compound (P) other than the polyamic acid ester (A) (described later) via Z ⁴ or Z ⁵ . It's okay.

[(C) Isocyanate compound]
In the embodiment, a monomer (isocyanate compound) having a photopolymerizable unsaturated bond can be optionally blended into the photosensitive resin composition in order to improve the resolution of the relief pattern. As such an isocyanate compound, a (meth)acrylic compound that undergoes a radical polymerization reaction with a photopolymerization initiator is preferable, and examples include, but are not limited to, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol dimethacrylate, etc. Mono- or di- or di-acrylates and methacrylates of glycol or polyethylene glycol, mono- or di- or di-acrylates and methacrylates of propylene glycol or polypropylene glycol, mono-, di- or triacrylates and methacrylates of glycerol, cyclohexane diacrylates and dimethacrylates, 1,4-butanediol diacrylates and dimethacrylates, diacrylates and dimethacrylates of 1,6-hexanediol, diacrylates and dimethacrylates of neopentyl glycol, mono- or diacrylates and methacrylates of bisphenol A, benzene trimethacrylate, isobornyl acrylate and methacrylate, Acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane triacrylate and methacrylate, di- or tri-acrylate and methacrylate of glycerol, di-, tri-, or tetra-acrylate and methacrylate of pentaerythritol, and ethylene oxide or propylene oxide of these compounds. Compounds such as adducts can be mentioned.

The blending amount of the isocyanate compound is preferably 1 part by mass to 50 parts by mass, more preferably 0.5 parts by mass to 30 parts by mass, based on 100 parts by mass of the polyamic acid ester (A).

Further, in order to obtain a cured product having a lower dielectric constant and a lower dielectric loss tangent, it is preferable to use an isocyanate compound (C') represented by the following general formula (20) as the isocyanate compound.

［式中、Ｒ^２３は水素原子又はメチル基を表し、Ｒ^２４は、置換基を有してもよく、酸素原子によって中断されていてもよい炭素原子数１乃至５のアルキレン基を表し、Ｒ^２５は、イソシアネート基又はブロックイソシアネート基を表す。］

[In the formula, ^R23 represents a hydrogen atom or a methyl group, ^R24 represents an alkylene group having 1 to 5 carbon atoms, which may have a substituent and may be interrupted by an oxygen atom, ²⁵ represents an isocyanate group or a blocked isocyanate group. ]

^R24 is not particularly limited as long as it is an alkylene group having 1 to 5 carbon atoms which may have a substituent and may be interrupted by an oxygen atom. Examples of the alkylene group having 1 to 5 carbon atoms include substituted or unsubstituted methylene group, ethylene group, propylene group, and butylene group. Examples of the alkylene group interrupted by an oxygen atom include -CH2-O-CH ₂ -, -C ₂ H ₄ -O-CH ₂ -, -CH ₂ -O-C ₂ H ₄ -, and the like. Examples of the substituent include a halogen atom, an acryloyl group, a methacryloyl group, a nitro group, an amino group, a cyano group, a methoxy group, and an acetoxy group, with an acryloyl group and a methacryloyl group being preferred.

R ²⁵ represents an isocyanate group or a blocked isocyanate group. An isocyanate group refers to a group represented by -NCO, and a blocked isocyanate group is a group in which an isocyanate group is blocked with a thermally removable protecting group, that is, a group in which an isocyanate blocking compound (blocking agent) is applied to the isocyanate group. Refers to the reacted group.

Blocking agents for isocyanate groups generally react with isocyanate groups to prevent reactions with functional groups (e.g., acid functional groups) in other molecules at room temperature, but desorb at high temperatures and block the isocyanate groups. refers to something that can be regenerated and made available for subsequent reaction (eg with acid functional groups).
Examples of blocking agents include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N,N-dimethylaminoethanol, 2-ethoxyethanol, and cyclohexanol, phenol, and o-nitrophenol. , p-chlorophenol, o-cresol, m-cresol, p-cresol and other phenols, ε-caprolactam and other lactams, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, etc. Oximes, amines, amides, nitrogen-containing heteroaryl compounds such as pyrazole, 3,5-dimethylpyrazole, and 3-methylpyrazole, thiols such as dodecanethiol and benzenethiol, malonic acid diester, acetoacetic acid ester, malon Active methylene compounds such as acid dinitrile, acetylacetone, methylene disulfone, dibenzoylmethane, dipivaloylmethane, and acetone dicarboxylic acid diester, hydroxamic acid esters, and the like can be mentioned.
Advantageously, the blocking agent is volatile and evaporates from the composition after desorption.

［式中、Ａは、アルコール、アミン、アミド、活性メチレン化合物、窒素含有ヘテロアリール化合物、オキシム、ケトオキシム、及びヒドロキサム酸エステルからなる群より選択されるイソシアネートブロック用化合物の残基を表す。］
で表される。 Blocked isocyanate groups are, for example,

[wherein A represents the residue of an isocyanate blocking compound selected from the group consisting of alcohols, amines, amides, active methylene compounds, nitrogen-containing heteroaryl compounds, oximes, ketoximes, and hydroxamic acid esters. ]
It is expressed as

Specific examples of the isocyanate compound represented by the general formula (20) include isocyanate-containing (meth)acrylates such as 2-isocyanate ethyl methacrylate and 2-isocyanate ethyl acrylate, and methyl ethyl ketone oxime, ε-caprolactam, 3, Examples include compounds to which blocking agents such as 5-dimethylpyrazole and diethyl malonate are added. In addition, these compounds may be used individually or in combination of 2 or more types.

The isocyanate compound (C') can be synthesized by a known method, or the commercially available products listed below can be used.
Karenz AOI (2-isocyanatoethyl acrylate manufactured by Showa Denko K.K., registered trademark),
Karenz AOI-VM (2-isocyanatoethyl acrylate manufactured by Showa Denko K.K., registered trademark),
Karenz MOI (2-isocyanatoethyl methacrylate manufactured by Showa Denko K.K., registered trademark),
Karenz MOI-BM (2-(O-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate, registered trademark, manufactured by Showa Denko K.K.),
Karenz MOI-BP (2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate, registered trademark, manufactured by Showa Denko K.K.),
Karens MOI-EG (manufactured by Showa Denko K.K., registered trademark),
Karenz BEI (1,1-(bisacryloyloxymethyl)ethyl isocyanate, registered trademark manufactured by Showa Denko K.K.),
Karenz AOI-BM (2-(O-[1′-methylpropylideneamino]carboxyamino)ethyl acrylate, registered trademark, manufactured by Showa Denko K.K.).
Among these, 2-(O-[1'-methylpropylideneamino]carboxyamino)ethyl acrylate (e.g., Karenz AOI-BM) and 1,1-(bisacryloyloxymethyl)ethyl isocyanate (e.g., Karenz BEI) is preferably used.

Furthermore, an isocyanate compound having a blocked isocyanate group having the following structure can be used.

The amount of the (C') isocyanate compound in the photosensitive resin composition according to the present invention is usually 1 part by mass to 50 parts by mass based on 100 parts by mass of the polyamic acid ester (A).

[(P) Polymeric compound other than the polyamic acid ester (A)]
In an embodiment, the photosensitive resin composition may further contain a resin component other than the polyamic acid ester (A). Examples of the resin component that can be contained in the photosensitive resin composition include polyimide, polyoxazole, polyoxazole precursor, phenol resin, polyamide, epoxy resin, siloxane resin, and acrylic resin.
The blending amount of these resin components is preferably in the range of 0.01 parts by mass to 20 parts by mass based on 100 parts by mass of polyamic acid ester (A).

[Other ingredients]
In embodiments, the photosensitive resin composition may further contain components other than the above-mentioned (A), (B), (C), and (P) components. Examples of other components include a photopolymerization initiator, a solvent, a sensitizer, an adhesion aid, a thermal polymerization inhibitor, an azole compound, a hindered phenol compound, and a filler.

Thermal crosslinking agents include hexamethoxymethylmelamine, tetramethoxymethylglycoluril, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril, and 1,3,4,6-tetrakis(butoxymethyl). ) glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea and 1,1, Examples include 3,3-tetrakis(methoxymethyl)urea.
Examples of fillers include inorganic fillers, and specific examples include sols of silica, aluminum nitride, boron nitride, zirconia, alumina, and the like.

The photosensitive resin composition of the present invention can contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it has absorption in the light source used during photocuring, but examples include tert-butylperoxy-iso-butyrate, 2,5-dimethyl-2,5-bis(benzoyl dioxy)hexane, 1,4-bis[α-(tert-butyldioxy)-iso-propoxy]benzene, di-tert-butylperoxide, 2,5-dimethyl-2,5-bis(tert-butyldioxy)hexenehydro Peroxide, α-(iso-propylphenyl)-iso-propylhydroperoxide, tert-butyl hydroperoxide, 1,1-bis(tert-butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4-bis (tert-butyldioxy)valerate, cyclohexanone peroxide, 2,2',5,5'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-amylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3'-bis(tert-butyl) Organic peroxides such as (peroxycarbonyl)-4,4'-dicarboxybenzophenone, tert-butyl peroxybenzoate, di-tert-butyl diperoxyisophthalate; 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone , octamethylanthraquinone, 1,2-benzanthraquinone, and other quinones; benzoin methyl, benzoin ethyl ether, α-methylbenzoin, α-phenylbenzoin, and other benzoin derivatives; 2,2-dimethoxy-1,2-diphenylethane; 1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy -2-Methyl-1-propan-1-one, 2-hydroxy-1-[4-{4-(2-hydroxy-2-methyl-propionyl)benzyl}-phenyl]-2-methyl-propane-1- one, phenylglyoxylic acid methyl ester, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl )-1-butanone, alkylphenone compounds such as 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one; bis(2 , 4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; 2-(O-benzoyloxime)-1-[4-(phenylthio) ) phenyl]-1,2-octanedione, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone, and other oxime esters Examples include compounds.
The above photopolymerization initiators are available as commercial products, such as IRGACURE 651, 184, 2959, 127, 907, 369, 379EG, 819, 819DW, 1800, 1870, 784, OXE01, OXE02, 250, 1173, MBF, TPO, 4265, TPO (manufactured by BASF), KAYACURE DETX, MBP, DMBI, EPA, OA (manufactured by Nippon Kayaku Co., Ltd.), VICURE-10, 55 (manufactured by STAUFER Co. Ltd.), ESACURE KIP150, TZT, 1001, KTO46, KB1, KL200, KS300, EB3, Triazine-PMS, Triazine A, Triazine B (manufactured by Nippon Siberhegner Co., Ltd.), ADEKA Optomer N-1717, ADEKA N-1414, ADEKA N-1606 (all manufactured by ADEKA Co., Ltd.) ). These photopolymerization initiators may be used alone or in combination of two or more.
The amount of the photopolymerization initiator is usually 0.1 parts by mass to 20 parts by mass, and preferably 0.5 parts by mass to 15 parts by mass from the viewpoint of photosensitivity characteristics, per 100 parts by mass of the polyamic acid ester (A). Department. When 0.1 parts by mass or more of the photopolymerization initiator is blended with respect to 100 parts by mass of the polyamic acid ester (A), the photosensitivity of the photosensitive resin composition tends to improve, while on the other hand, when it is blended with 20 parts by mass or less. It is easy to improve the thick film curability of the photosensitive resin composition.

As the solvent, it is preferable to use an organic solvent from the viewpoint of solubility in the polyamic acid ester (A). Specifically, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, γ-butyrolactone. , α-acetyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, ethyl lactate, etc., which may be used alone or in combination of two or more. be able to.

The above solvent may be used in an amount ranging from 30 parts by mass to 1500 parts by mass, preferably 100 parts by mass, based on 100 parts by mass of (A) polyamic acid ester, depending on the desired coating film thickness and viscosity of the photosensitive resin composition. It can be used in a range of 1000 parts by mass.

In embodiments, a sensitizer can be optionally added to the photosensitive resin composition in order to improve photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, and 2,6-bis(4'-diethylaminobenzal). ) Cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinna Mylideneindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7- Diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2- Mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylamino) (styryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, and the like. These can be used alone or in combination.

The amount of the sensitizer to be blended is preferably 0.1 parts by mass to 25 parts by mass based on 100 parts by mass of the polyamic acid ester (A).

In the embodiment, an adhesion aid can be optionally blended into the photosensitive resin composition in order to improve the adhesion between the film formed using the photosensitive resin composition and the base material. Examples of adhesive aids include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl) ) Succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene- Silanes such as 1,4-bis(N-[3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, and N-phenylaminopropyltrimethoxysilane Coupling agents, aluminum-based adhesion aids such as aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), ethyl acetoacetate aluminum diisopropylate, and the like.

Among these adhesion aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesive strength. The blending amount of the adhesion aid is preferably in the range of 0.5 parts by mass to 25 parts by mass based on 100 parts by mass of the polyamic acid ester (A).

In the embodiment, a thermal polymerization inhibitor can be optionally added in order to improve the stability of the viscosity and photosensitivity of the photosensitive resin composition during storage, particularly in the state of a solution containing a solvent. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, , 6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl- N-sulfopropylamino)phenol, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, etc. are used.

The blending amount of the thermal polymerization inhibitor is preferably in the range of 0.005 parts by mass to 12 parts by mass based on 100 parts by mass of the polyamic acid ester (A).

For example, when using a substrate made of copper or a copper alloy, an azole compound can be optionally blended into the photosensitive resin composition in order to suppress discoloration of the substrate. Examples of azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl -5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, Hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3, 5-bis(α,α-dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl -2-hydroxyphenyl)-benzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, Hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5- Examples include methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, and 1-methyl-1H-tetrazole. Particularly preferred are tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. Further, these azole compounds may be used alone or in a mixture of two or more.

The blending amount of the azole compound is 0.00 parts by mass based on 100 parts by mass of (A) polyamic acid ester.
The amount is preferably 1 part by mass to 20 parts by mass, and more preferably 0.5 parts by mass to 5 parts by mass from the viewpoint of photosensitivity characteristics. When the blending amount of the azole compound is 0.1 parts by mass or more based on 100 parts by mass of the polyamic acid ester (A), when the photosensitive resin composition is formed on copper or copper alloy, copper or copper alloy It is preferable that the amount is 20 parts by mass or less, since discoloration of the surface is suppressed and the photosensitivity is excellent.

In embodiments, a hindered phenol compound can optionally be blended into the photosensitive resin composition to suppress discoloration on copper. Examples of hindered phenol compounds include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl -4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3 -t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2 -thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydro) cinnamamide), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), pentaerythrityl-tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5 -trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl) )-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl )-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl )-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6 -dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethylmethyl-3-hydroxy-2,6- dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl )-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6- trimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy- 2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl- 3-Hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6- Ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t- Butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris( 4-t-butyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4- t-Butyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4- t-Butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2
, 4,6-(1H,3H,5H)-trione, etc., but are not limited thereto. Among these, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H )-trione is particularly preferred.

The blending amount of the hindered phenol compound is preferably 0.1 parts by mass to 20 parts by mass, and from the viewpoint of photosensitivity characteristics, 0.5 parts by mass to 10 parts by mass, based on 100 parts by mass of polyamic acid ester (A). It is more preferable that it is part. When the blending amount of the hindered phenol compound to 100 parts by mass of (A) polyamic acid ester is 0.1 part by mass or more, for example, when the photosensitive resin composition is formed on copper or copper alloy, copper or copper Discoloration and corrosion of the alloy are prevented, and on the other hand, when the amount is 20 parts by mass or less, the photosensitivity is excellent, which is preferable.

[Metal removal filter]
The present invention is a metal removal method for removing metal impurities in a photosensitive resin composition solution using a metal removal filter, and the metal removal filter includes a porous membrane made of ultra-high molecular weight polyethylene, and a porous membrane. and a resin layer disposed to cover at least a portion of the resin layer, and the resin contained in the resin layer has a neutral group or an ion exchange group.
The ultra-high molecular weight polyethylene is not particularly limited, and any known ultra-high molecular weight polyethylene can be used. Ultra-high molecular weight means that the weight average molecular weight is 1.0×10 ⁶ or more, and the molecular weight of ultra-high molecular weight polyethylene is not particularly limited, but is generally 1.0×10 ⁶ to 7.0. ×10 ⁷ is preferred, and 1.0 × 10 ⁶ to 7.0 × 10 ⁶ is more preferred. In the present invention, the molecular weight of ultra-high molecular weight polyethylene means the one measured by gel permeation chromatography (GPC).

The metal removal filter has a resin layer disposed to cover at least a portion of the surface of the porous membrane. The resin layer contains a resin, and the resins include polyamides such as 6-nylon and 6,6-nylon; polyolefins such as polyethylene and polypropylene; polystyrene; polyimide; polyamideimide; poly(meth)acrylate; polytetrafluoroethylene. , perfluoroalkoxy alkanes, perfluoroethylene propene copolymers, ethylene-tetrafluoroethylene copolymers, ethylene-chlorotrifluoroethylene copolymers, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride; polyfluorocarbons; polyvinyl alcohol; polystyrene Cellulose; Cellulose acetate; Polystyrene; Polysulfone; Polyethersulfone.

Further, the resin in the resin layer may be bonded to the porous membrane. That is, the resin in the resin layer may be chemically bonded to the porous membrane, and the resin layer may have graft chains.
The resin layer is preferably arranged to cover at least 50%, preferably 70% or more, more preferably 100% of the porous membrane.

Having a graft chain means that molecules different from the ultra-high molecular weight polyethylene of the backbone polymer are chemically bonded on at least a portion of the surface (preferably 50% or more, more preferably 70% or more) of the porous membrane. means state. The surface of the porous membrane also includes the surface of the pores.

As such a metal removal filter, for example, Purasol ^TM from Nippon Entegris Co., Ltd.
Examples include a purifier for SP solvents and a purifier for ^SN solvents manufactured by Nippon Entegris Co., Ltd., and these can also be used in combination.

The metal impurities to be removed from the solution are mainly metals other than alkali metals and alkaline earth metals, but are not limited thereto. For example, polyvalent metal elements, their ions, their hydroxide colloids, and their oxide colloids are objects to be adsorbed and removed. These are colloidal substances in which the metal is in the second period to the sixth period, and are polyvalent metal elements of groups 1 to 14, polyvalent metal ions, or metal hydroxides or metal oxides thereof. When a polyvalent metal element is used as a catalyst, a zero-valent metal may remain as a metal in the product without being ionized.
These metal impurities are ionic and particulate. Ionic metal impurities are easy to remove with ion exchange resin, but particulates remain, and particulate metal impurities can be removed with a filter. However, in this case, ionic impurities tend to remain. In the method for removing metal impurities of the present invention, both ionic and particulate metal impurities can be efficiently removed by using a specific filter, although the reason is not clear.

[Method for producing purified material solution with reduced metal impurities]
The present invention includes a step of preparing a solution of the material to be purified by dissolving the material to be purified in a liquid, a step of filling the solution of the material to be purified into a filtration device using the above metal removal filter, and a step of filtering the material to be purified. The process consists of removing metal.
As a liquid feeding method for a filtration device using a metal removal filter, a pressurized type, a pump, or a motor can be used. Moreover, as a liquid contact member in the filter, a container coated with PTFE, PFA, or Teflon, which does not elute metals, is preferable.

The materials to be refined are metal impurities that are naturally present in the substances used as raw materials, metal impurities that still remain after purification treatment, and metal impurities that are used as catalysts when synthesizing the raw materials. Examples include materials containing metal impurities.
In particular, since the material to be purified of the present invention contains polyamic acid ester, a general method for removing metals may be to use a microporous sulfonic acid ion exchange resin to remove impurities. This method is difficult to apply because it causes modification of the ester, and the method of the present invention is particularly effective. This polyamic acid ester contains impurities such as metals such as Na, K, Al, Cr, Cu, Fe, Ni, and Pb, their metal ions, metal hydroxides, and colloids of metal oxides, and these metal impurities are completely eliminated. The metal removal method of the invention can remove impurities and reduce impurities.

A solution of the material to be purified, which is obtained by dissolving the material to be purified in a liquid, contains several ppm to several hundred ppm of metal impurities derived from the material to be purified, and the metal removal method of the present invention is applied to the solution. By doing so, the solution can be applied until the metal impurities in the solution are reduced to several ppb to 1000 ppb or less, preferably several ppb to several hundred ppb or less, and more preferably several ppb to several tens of ppb or less.

In the present invention, the liquid (organic solvent) that dissolves the material to be purified can be a previously purified liquid (or referred to as a pretreatment liquid). When a solution of the material to be purified (composition solution before purification) is obtained by using the pretreatment liquid, a purified material solution (composition solution after purification) in which impurities are highly reduced can be obtained more efficiently.

The purified material solution with reduced impurities can be obtained by removing the solvent from the purified material solution. Further, the purified material solution with reduced impurities can be used as it is as a composition solution containing the material.

The material for the filter used in the present invention is preferably PE or PTFE. PTFE is most preferred, but the type of membrane is not limited.
The smaller the pore size of the filter, the higher the efficiency of removing metal impurities, so it is preferable, but if it is too small, the filtration will be poor. Considering the viscosity of the material solution to be purified, it is preferably 10 μm to 0.2 μm, and 1 μm to 0. .2 μm is more preferable.

When the solution of the material to be purified is a solution containing an organic solvent, examples of the liquid (ie, solvent) that dissolves the material to be purified include water; n-pentane, i-pentane, n-hexane. , i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, methylcyclohexane, and other aliphatic hydrocarbon solvents; benzene, toluene, xylene, ethylbenzene , aromatic hydrocarbon solvents such as trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene, trimethylbenzene; Methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t- Pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n- Nonyl alcohol, 4-methyl-2-pentanol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, Monoalcoholic solvents such as cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol, methylisobutylcarbinol; ethylene glycol, propylene glycol, 1, 3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, Polyhydric alcohol solvents such as dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n -Pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, diacetone alcohol Ketone solvents such as , acetophenone, methylpropyl ketone, methylbutylketone, 2-heptanone, 3-heptanone, 4-heptanone, and Fencheon; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2- Ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether , ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, Diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxy triglycol, tetraethylene glycol di-n-butyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono Ether solvents such as ethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran; diethyl carbonate, methyl formate, ethyl formate, propyl formate, isopropyl formate, formic acid Butyl, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate , n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl acetate, diethylene glycol mono-n-butyl acetate, propylene glycol monomethyl ether acetate , propylene glycol monoethyl acetate, propylene glycol monopropyl ether, propylene glycol monobutyl acetate, dipropylene glycol monomethyl acetate, dipropylene glycol monoethyl acetate, glycol diacetate, methoxytriglycol acetate, methyl propionate, propion Ethyl acid, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl butyrate, ethyl butyrate, butyric acid Propyl, isopropyl butyrate, butyl butyrate, isobutyl butyrate, methyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate , ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate , methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl 3-methoxypropionate, 3-methyl Ester solvents such as -3-methoxybutylpropionate and 3-methyl-3-methoxybutylbutyrate; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate , methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl Acetate solvents such as -3-methoxybutyl acetate; N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide , N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and other nitrogen-containing solvents; sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone. Examples include solvents and the like. These solvents may be used alone or in combination of two or more. Among the above-mentioned solvents, especially those such as 4-methyl-2-pentanol and methylisobutylcarbinol Alcohol solvents; Polyhydric alcohol solvents such as propylene glycol; Aromatic hydrocarbon solvents such as toluene and xylene; Ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol Ethers such as diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether System solvents: ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate , isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, 3 - Methyl methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, methyl acetoacetate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, Ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, Ester solvents such as 3-methyl-3-methoxybutylpropionate and 3-methyl-3-methoxybutylbutyrate; methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoether ether acetate, propylene Glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl propyl ketone, methyl butyl ketone, 2 -Ketone solvents such as heptanone, 3-heptanone, 4-heptanone; N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, N-methyl-2- Nitrogen-containing solvents such as pyrrolidone and N-ethyl-2-pyrrolidone are preferred.

Furthermore, most preferred are tetrahydrofuran, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, cyclohexanone, and cyclopentanone.

The metal removal method by filtration using a metal removal filter in the present invention can also be applied at the stage of the polyamic acid ester solution, that is, at the stage where the polyamic acid is dissolved in the organic solvent described above, and various additives can be added. However, it can also be applied at the stage where the photosensitive resin composition is made into a solution. Further, both steps can be carried out in combination.

A polyamic acid ester was synthesized using the following synthesis procedure. The weight average molecular weights shown in the following synthesis examples of this specification are the results of measurement by gel permeation chromatography (hereinafter abbreviated as GPC in this specification). A GPC device (HLC-8320GPC) manufactured by Tosoh Corporation was used for the measurement, and the measurement conditions were as follows.
GPC column: KD-803, KD-805 (manufactured by Shodex)
Column temperature: 50℃
Solvent: N,N-dimethylformamide (Kanto Kagaku, special grade), lithium bromide monohydrate (Kanto Kagaku, special grade) (30mM) / phosphoric acid (Aldrich) (30mM) / tetrahydrofuran (Kanto Kagaku, special grade) ( 1%)
Flow rate: 1.0 mL/min Standard sample: Polystyrene (manufactured by GL Sciences)

In the measurements of the NMR spectra shown in the Examples below in this specification, the 1H-NMR spectra were measured using JNM-ECX500 (500 MHz, manufactured by JEOL Ltd.).

<Production Example 1> Synthesis of dicarboxylic acid diester (1) 200.00 g (0.68 mol) of 4,4'-biphthalic dianhydride (Tokyo Kasei Kogyo Co., Ltd.) was placed in a 2-liter four-necked flask, and - Add 176.92 g (1.366 mol) of hydroxyethyl methacrylate (Aldrich), 0.74 g (0.007 mol) of hydroquinone (Tokyo Kasei Kogyo Co., Ltd.) and 600 g of γ-butyrolactone (Kanto Kagaku, Shika special grade) and heat at 23°C. After stirring and adding 108.63 g (1.36 mol) of pyridine (Kanto Kagaku, Dehydrated), the temperature was raised to 50°C, and by stirring at 50°C for 2 hours, a dicarboxylic acid represented by the following formula (9) was obtained. A solution containing diester (1) was obtained.

<Production Example 2> Synthesis of Polymer (2) as Polyamic Acid Ester 82.46 g of the solution prepared in Production Example 1 and 19.45 g of γ-butyrolactone were placed in a 500 ml four-necked flask, and heated at about 5°C with N. , N'-diisopropylcarbodiimide (DIC, Tokyo Chemical Industry Co., Ltd.) 13.13 g dissolved in 30 g of γ-butyrolactone was added dropwise to the reaction solution over 0.5 hours while stirring, and after the dropwise addition, for 0.5 hours. Stirred. Next, 19.68 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (Tokyo Kasei Kogyo Co., Ltd.) was dissolved in 30 g of N-methyl-2-pyrrolidinone (Kanto Kagaku, Shika Special Grade). The mixture was added dropwise over 2 hours while stirring. After that, the temperature was raised to about 25°C, and after stirring for 6 hours, 4.5 g of ethanol (Kanto Kagaku, special grade) was added and stirred for 1 hour.

The resulting reaction mixture was added to 1500 g of methanol (Kanto Kagaku, special grade) to form a precipitate consisting of a crude polymer. The supernatant liquid was decanted to separate the crude polymer, which was dissolved in 150.0 g of N-methyl-2-pyrrolidinone to obtain a crude polymer solution. The resulting crude polymer solution was dropped into 2250 g of water to precipitate the polymer, and the resulting precipitate was filtered, washed twice with 600 g of methanol, and vacuum dried to obtain powdered polymer (2). Obtained. When the molecular weight of Polymer (2) was measured by GPC (standard polystyrene conversion), the weight average molecular weight (Mw) was 8,016. The yield was 73.6%. This reaction product polymer (2) has a repeating unit structure represented by the following formula (10).

<Example> Creation of photosensitive resin composition solution 28.5714 g of polymer (2) obtained in Production Example 2, 1.71 g of IRGACURE [registered trademark] OXE01 (manufactured by BASF, photopolymerization initiator), AOI-BM (Showa Denko Co., Ltd., 2-(O-[1'-methylpropylideneamino]carboxyamino)ethyl acrylate) 8.57 g, KBM-5103 (Shin-Etsu Chemical Co., Ltd., 3-acryloxypropyltrimethoxysilane) ), 0.43 g of IRGANOX [registered trademark] 3114 (manufactured by BASF, hindered phenolic antioxidant), and 0.28 g of phthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 48.00 g of cyclohexanone, ethyl A composition was prepared by dissolving lactate in 12.00 g. Thereafter, it was filtered using a polypropylene microfilter with a pore size of 10 μm to prepare a negative photosensitive resin composition.

<Example 1> Process of removing metals by filtration The negative photosensitive resin composition of the solution to be purified prepared above was filtered using a Purasol ^™ SP solvent purifier capsule filter manufactured by Nippon Entegris. The pressure during filtration was 0.3 MPas. The metal content in the purified solution at the time of filtration of 100 g was measured using ICP-MS7500, and the metal analysis value in terms of solid content was calculated.

<Example 2> Metal removal step by filtration The negative photosensitive resin composition to be purified, which was prepared above, was filtered using a Purasol ^TM SN solvent purifier capsule filter manufactured by Nippon Entegris. The pressure during filtration was 0.3 MPas. The metal content in the purified solution at the time of filtration of 100 g was measured using ICP-MS7500, and the metal analysis value in terms of solid content was calculated.

<Example 3> Metal removal process by filtration After filtering the negative photosensitive resin composition of the solution to be purified as described above through a PTFE capsule filter with a pore size of 0.2 μm manufactured by Adbantec, a purifier capsule for Purasol ^TM SP solvents manufactured by Nippon Entegris was used. The mixture was filtered using a filter, and then filtered using a Purifier Capsule Filter for Purifier ^SN Solvents manufactured by Nippon Entegris. The pressure during filtration was 0.3 MPas. The metal content in the purified solution at the time of filtration of 100 g was measured using ICP-MS7500, and the metal analysis value in terms of solid content was calculated.

<Comparative Example 1> Metal removal process by filtration The negative photosensitive resin composition to be purified, which was prepared above, was filtered using a PP membrane filter manufactured by Loki Techno Co., Ltd. with a pore diameter of 10 μm. The pressure during filtration was 0.3 MPas. The metal content in the purified solution at the time of filtration of 100 g was measured using ICP-MS7500, and the metal analysis value in terms of solid content was calculated.

<Comparative Example 2> Metal removal step by filtration The negative photosensitive resin composition to be purified, which was prepared above, was filtered using a PP membrane filter manufactured by Loki Techno Co., Ltd. with a pore diameter of 5 μm. The pressure during filtration was 0.3 MPas. The metal content in the purified solution at the time of filtration of 100 g was measured using ICP-MS7500, and the metal analysis value in terms of solid content was calculated.

<Comparative Example 3> Metal removal process by filtration The negative photosensitive resin composition to be purified as described above was filtered using a PTFE membrane filter manufactured by Loki Techno Co., Ltd. with a pore diameter of 10 μm. The pressure during filtration was 0.3 MPas. The metal content in the purified solution at the time of filtration of 100 g was measured using ICP-MS7500, and the metal analysis value in terms of solid content was calculated.

<Comparative Example 4> Metal removal step by filtration The negative photosensitive resin composition to be purified as described above was filtered using a PTFE membrane filter manufactured by Loki Techno Co., Ltd. with a pore diameter of 3 μm. The pressure during filtration was 0.3 MPas. The metal content in the purified solution at the time of filtration of 100 g was measured using ICP-MS7500, and the metal analysis value in terms of solid content was calculated.

<Comparative Example 5> Metal removal process by filtration The negative photosensitive resin composition to be purified as described above was filtered using a PTFE membrane filter manufactured by Adbantec with a pore diameter of 1 μm. The pressure during filtration was 0.3 MPas. The metal content in the purified solution at the time of filtration of 100 g was measured using ICP-MS7500, and the metal analysis value in terms of solid content was calculated.

<Comparative Example 6> Metal removal step by filtration The negative photosensitive resin composition to be purified as described above was filtered using a PTFE capsule filter manufactured by Adbantec with a pore size of 0.2 μm. The pressure during filtration was 0.3 MPas. The metal content in the purified solution at the time of filtration of 100 g was measured using ICP-MS7500, and the metal analysis value in terms of solid content was calculated.

<Comparative Example 7> Metal removal step by filtration The solution to be purified prepared above The negative photosensitive resin composition was manufactured by Nippon Entegris Co., Ltd. with a pore size of 3 nm.
Filtration was performed using a PE capsule filter. The metal content of the purified liquid could not be calculated due to poor filtration.

The present invention provides highly purified photosensitive resin compositions by removing metal impurities in polyamic acid esters in photosensitive resin compositions used in the packaging process during semiconductor device manufacturing using a specific metal removal filter. It became possible to obtain.

Claims (8)

Metal impurities in the photosensitive resin composition are removed by filtration using a metal removal filter having a porous membrane made of ultra-high molecular weight polyethylene and a resin layer disposed to cover at least a portion of the porous membrane. Metal removal method to remove. 2. The metal removal method according to claim 1, wherein the photosensitive resin composition contains a polyamic acid ester, and the polyamic acid ester is a compound having a structural unit represented by the following general formula (1).

[In the formula, X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and R ¹ and R ² are each independently a monovalent organic group. ] The metal removal method according to claim 1 or 2, wherein the photosensitive resin composition is a solution containing an organic solvent. The metal impurities removed by filtration using the metal removal filter are those that belong to Group 1 in periods 2 to 6 of the periodic table according to the representation method established by the International Union of Pure and Applied Chemistry (IUPAC). The metal removal method according to any one of claims 1 to 3, wherein the metal removal method is a colloidal material of a metal of Group 14 to a polyvalent metal ion thereof, or a metal hydroxide or metal oxide thereof. A porous membrane made of ultra-high molecular weight polyethylene and a resin disposed to cover at least a portion of the porous membrane are used to remove metal impurities in an organic solution containing a compound having a structural unit represented by the following general formula (1). A method for removing metals by filtration using a metal removal filter having a layer.

[In the formula, X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and R ¹ and R ² are each independently a monovalent organic group. ] The metal impurities removed by filtration using the metal removal filter are those that belong to Group 1 in periods 2 to 6 of the periodic table according to the representation method established by the International Union of Pure and Applied Chemistry (IUPAC). 6. The metal removal method according to claim 5, wherein the metal is a colloidal material of a metal of Group 14 to a polyvalent metal ion thereof, or a metal hydroxide or metal oxide thereof. In the photosensitive resin composition obtained using the metal removal method described in claims 1 to 4, IUPAC (International Union of Pure and Applied Chemistry)
colloidal substances of Group 1 to Group 14 metals, their polyvalent metal ions, or their metal hydroxides or metal oxides in the 2nd to 6th period according to the notation method specified by Pure and Applied Chemistry) A purified photosensitive resin composition containing 100 to 1000 ppt of In the organic solution obtained using the metal removal method according to claim 5 or 6, IUPAC (International Union of Pure and Applied Chemistry)
Colloidal substances of Group 1 to Group 14 metals, their polyvalent metal ions, or their metal hydroxides or metal oxides are Purified organic solution containing 100 to 1000 ppt.