JP4776485B2 - Photosensitive polyamic acid ester composition - Google Patents

Description

  The present invention relates to a photosensitive material useful for manufacturing electrical / electronic materials such as semiconductor devices and multilayer wiring boards, and a laminate in which a metal layer is provided on a heat-resistant resin layer. More specifically, the present invention is made of titanium or aluminum in contact with a layer composed of a polyamic acid ester composition capable of providing i-line exposure and having a polyimide pattern having high heat resistance and chemical resistance and a polyimide resin. The present invention relates to a laminate provided with layers.

Polyimide resin is attracting attention as a material related to microelectronics because of its high thermal and chemical stability, low dielectric constant, and excellent planarization ability, and is used as a semiconductor surface protective film or interlayer insulating film, or Widely used as a material for multi-chip modules.
In the case of manufacturing a semiconductor device using a polyimide resin, a polyimide resin film is usually formed on a substrate and a desired pattern is formed using a lithography technique. Specifically, an indirect pattern forming method is used in which a photoresist pattern is formed on a polyimide resin film using a photoresist and a photomask, and then polyimide resin is patterned by etching. . However, in this method, a photoresist pattern to be a mask is first formed on the polyimide resin film, then the polyimide resin is etched, and finally the unnecessary photoresist pattern is peeled off. Therefore, the process is complicated and the resolution is low because of indirect pattern formation. Moreover, since it is necessary to use a toxic substance such as hydrazine as a solvent for etching, there is also a safety problem.

In order to overcome the above problems, a method of introducing a photopolymerizable photosensitive group into a polyimide precursor and directly forming a pattern on the polyimide precursor film has been put into practical use. For example, a film made of a polyimide precursor formed by bonding a compound having a double bond to a polyamic acid derivative via an ester bond, an amide bond, or an ionic bond, and a photosensitive polyimide precursor composition containing a photoinitiator or the like. Forming a pattern using means for insolubilizing the polyimide precursor of the exposed portion of the coating film by exposing it through a photomask having a pattern, and subjecting it to a development treatment. A method for converting a polyimide precursor into a polyimide having thermal stability by removing the photosensitive group component by heating is proposed in Non-Patent Document 1 and the like. This technology is generally called photosensitive polyimide technology. This technique overcomes the problems associated with processes using the conventional non-photosensitive polyimide precursor described above. Therefore, the polyimide pattern is often formed by the above-described photosensitive polyimide technology.
Furthermore, by using an aromatic diamine having a specific structure as a raw material for the polyimide precursor and introducing an alkyl group at the specific position, the solubility in general-purpose organic solvents is improved, and it is highly resistant to light. A technique for making sensitivity is proposed in Patent Document 1. However, on the other hand, the cured relief pattern after curing is inferior in chemical resistance (see Comparative Example 3 described later).

In recent years, there has been a demand for improvement in resolution when forming a pattern of a polyimide film used in a semiconductor device or the like. In the process using the non-photosensitive polyimide before the development of the above-mentioned photosensitive polyimide technology, high resolution could not be obtained. Therefore, the semiconductor device and the manufacturing process were designed on the assumption that the semiconductor device was manufactured. The integration rate and accuracy were limited. On the other hand, when the photosensitive polyimide technology is used, a high resolution can be obtained at the time of pattern formation, so that a semiconductor device with a high integration rate and high accuracy can be manufactured. This will be described below.
For example, when manufacturing a memory element or the like, in order to increase the yield of a product, an operation is performed in which a spare circuit is made in advance and unnecessary circuits are cut after the product is inspected. In the process using conventional non-photosensitive polyimide, unnecessary circuit cutting was performed before the formation of the polyimide pattern, whereas in the process using photosensitive polyimide, the resolution at the time of polyimide pattern formation is high, A hole for cutting an unnecessary circuit in the pattern is provided, and the preliminary circuit can be cut after the polyimide pattern is formed. Therefore, it becomes possible to cut the spare circuit at a stage closer to the completion time of the final product, and a higher product yield is achieved.

  When a hole for cutting unnecessary circuits is provided in the polyimide pattern, it is desired to make the hole smaller in order to achieve high integration of the semiconductor device. There is a need for photosensitive polyimide precursors that can be patterned with resolution. In addition, when a photosensitive polyimide precursor that enables high-resolution pattern formation is used in the semiconductor device manufacturing process, a wide process margin necessary for high integration and high accuracy of the semiconductor device can be achieved. Here, the “wide process margin” means that usable conditions for exposure and development (for example, conditions such as time and temperature) for pattern formation in the process are wide. Therefore, the higher the resolution at the time of forming the polyimide pattern, the better. The above also applies when the polyimide pattern is used for other semiconductor devices (multichip module or the like). For this reason, there is an increasing demand for a photosensitive polyimide precursor composition having a high resolution that enables formation of a highly accurate pattern.

  By the way, a semiconductor device (hereinafter also referred to as “element”) is mounted on a printed circuit board by various methods in accordance with purposes. A common element is a wire bonding method in which a thin wire is connected from an external terminal (pad) of the element to a lead frame. However, as the speed of the element has increased and the operating frequency has reached GHz, in today's packaging, The difference in the wiring length between the terminals has led to the influence of the device operation. For this reason, when mounting elements for high-end applications, it is necessary to accurately control the length of the mounting wiring, and wire bonding makes it impossible to meet the requirements.

  Therefore, flip chip mounting has been proposed in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed thereon, the chip is turned over (flip), and mounted directly on a printed board. Flip chip mounting is used for high-end devices that handle high-speed signals because the wiring distance can be accurately controlled, and because of the small mounting size, the demand is rapidly expanding. When polyimide is used for flip chip mounting, the polyimide resin is required to have resistance to a resist stripping solution at a high temperature and heat resistance that can withstand solder reflow. Therefore, in addition to the excellent pattern formability and heat resistance as described above, the photosensitive polyimide resin for the material of the rewiring layer has performance such as chemical resistance to the resist stripping solution used in the process. It is important. Further, there is an increasing demand for using i-line as an exposure source when forming a pattern.

Therefore, a photosensitive polyimide that can form a pattern by i-line and has both heat resistance and chemical resistance has been required. As an example, a technique for imparting heat resistance and chemical resistance to a polyimide precursor that can be patterned by i-line using a methylmelamine-based crosslinking agent, a methylurea-based crosslinking agent, or the like has been proposed. However, as a result of investigations by the present inventors, it has been found that there is a case in which an adverse effect that metal wiring such as Al and Ti becomes difficult to adhere to polyimide due to curing of the polyimide surface state by crosslinking.
Therefore, there is a need for a photosensitive polyimide that can form a pattern by the above-mentioned i-line without using a cross-linking agent, and has a high heat resistance and chemical resistance in a cured polyimide pattern. However, a photosensitive polyimide precursor composition that forms such an excellent polyimide has not been known so far.

Japanese Patent No. 2693168 Yamaoka, Otomo, "Polyfile", 1990, 27, No. 2, pp. 14-18

  An object of this invention is to provide the photosensitive polyamic-acid ester composition which can give the polyimide pattern which can be i-line-exposed and has both high heat resistance and chemical resistance. Another object of the present invention is to provide a laminate comprising a relief pattern obtained by curing the composition and a metal layer, and a laminate having high adhesion, chemical resistance, and heat resistance at the same time, and a method for producing the laminate. And

  The present inventors have intensively studied to develop a photosensitive polyimide precursor composition that can be used to form a polyimide pattern having excellent target characteristics. As a result, when used as a raw material for polyimide, i-line exposure is possible and high heat resistance is achieved by using a photosensitive composition comprising a polyamic acid ester comprising a specific repeating unit, a photoinitiator, and a solvent. It was found that a photosensitive polyamic acid ester composition capable of giving a polyimide pattern having both properties and chemical resistance was obtained. The present invention has been made based on these new findings.

〔式中、Ｘは１個のベンゼン環を含む４価の芳香族基、または２個のベンゼン環が単結合した４価の芳香族基であり、Ｘ’は１個もしくは２個のベンゼン環を含む４価の芳香族基である。０．５≦ｍ／（ｍ＋ｎ）≦１．０である。ＲおよびＲ’はそれぞれ独立してオレフィン性二重結合を有する１価の基であり、同一であっても異なっていても良い。ＹおよびＹ’は下記一般式（２）で表される２価の芳香族基であり、同一であっても異なっていても良い。

（式中、Ａは炭素数が１〜４までの２価の脂肪族基であり、式中、Ｂは炭素数が１〜４までの１価の脂肪族基である。）〕 That is, the first of the present invention is (A) with respect to 100 parts by mass of a polyamic acid ester composed of a repeating unit represented by the following general formula (1), (B) 1 to 15 parts by mass of a photoinitiator, C) A photosensitive polyamic acid ester composition comprising 30 to 600 parts by mass of a solvent.

[Wherein X is a tetravalent aromatic group containing one benzene ring, or a tetravalent aromatic group in which two benzene rings are single-bonded, and X ′ is one or two benzene rings. Is a tetravalent aromatic group. It is 0.5 <= m / (m + n) <= 1.0. R and R ′ are each independently a monovalent group having an olefinic double bond and may be the same or different. Y and Y ′ are divalent aromatic groups represented by the following general formula (2), which may be the same or different.

(In the formula, A is a divalent aliphatic group having 1 to 4 carbon atoms, and B is a monovalent aliphatic group having 1 to 4 carbon atoms.)]

The second of the present invention is a layer comprising a cured relief pattern obtained by curing a photosensitive polyamic acid ester composition having a repeating unit represented by the general formula (1), and titanium and aluminum in contact with the layer. It is a laminated body characterized by having at least one metal layer selected from the group consisting of:
Furthermore, the third of the present invention is to form a coating film on the substrate by applying the photosensitive polyamic acid ester composition having the repeating unit represented by the general formula (1) to the substrate and drying it. A step of irradiating the coating film with ultraviolet rays directly through a photomask having a pattern, or by developing with a developer to remove an unexposed portion of the coating film on the substrate. A step of forming a relief pattern; a step of forming a layer of a cured relief pattern of a polyimide resin by heating the relief pattern on the substrate; at least one selected from argon, oxygen, and carbon tetrafluoride A step of dry etching the surface of the layer with a seed gas, and at least one metal layer selected from the group consisting of titanium and aluminum in contact with the layer A step of forming a method for producing a laminate, characterized in that it consists of.

  According to the present invention, a photosensitive polyamic acid ester composition capable of providing a polyimide pattern capable of i-line exposure and having both high heat resistance and chemical resistance can be provided. Also provided are a laminate comprising a relief pattern obtained by curing the composition and a metal layer, and simultaneously having high adhesion, chemical resistance and heat resistance, and a method for producing the laminate. be able to.

（式中、Ｘは１個のベンゼン環を含む４価の芳香族基、または２個のベンゼン環が単結合した４価の芳香族基であり、Ｘ’は１個もしくは２個のベンゼン環を含む４価の芳香族基である。０．５≦ｍ／（ｍ＋ｎ）≦１．０である。ＲおよびＲ’はそれぞれ独立してオレフィン性二重結合を有する１価の基であり、同一であっても異なっていても良い。ＹおよびＹ’は下記一般式（２）で表される２価の芳香族基であり、同一であっても異なっていても良い。 Hereinafter, embodiments of the present invention will be described in detail.
<Photosensitive polyamic acid ester composition>
(A) Polyamic acid ester The polyamic acid ester which is a component of the composition of the present invention is a polyamic acid ester composed of a repeating unit represented by the following general formula (1). Examples of the tetracarboxylic dianhydride include , Pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride can be used, and examples of the diamine include 3,3′-dimethyl-4,4′-diamino Diphenylmethane can be used and can be produced by subjecting both to a condensation reaction. These tetracarboxylic dianhydrides and diamines can be used alone or in combination of two or more.

(In the formula, X is a tetravalent aromatic group containing one benzene ring or a tetravalent aromatic group in which two benzene rings are single-bonded, and X ′ is one or two benzene rings. A tetravalent aromatic group containing 0.5 ≦ m / (m + n) ≦ 1.0 R and R ′ are each independently a monovalent group having an olefinic double bond, Y and Y ′ are divalent aromatic groups represented by the following general formula (2), which may be the same or different.

（式中、Ａは炭素数が１〜４までの２価の脂肪族基であり、式中Ｂは炭素数が１〜４までの１価の脂肪族基である。）〕
上記ポリアミド酸エステルにおいて、その繰り返し単位中のＸ基は、原料として用いるテトラカルボン二無水物に由来する。該テトラカルボン酸二無水物の例としては、ピロメリット酸二無水物、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物が挙げられる。これらのテトラカルボン酸二無水物は、１種あるいは２種以上を混合して用いることができる。

(In the formula, A is a divalent aliphatic group having 1 to 4 carbon atoms, and B is a monovalent aliphatic group having 1 to 4 carbon atoms.)]
In the polyamic acid ester, the X group in the repeating unit is derived from a tetracarboxylic dianhydride used as a raw material. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.

  In the polyamic acid ester, X ′ in the repeating unit is derived from tetracarboxylic dianhydride used as a raw material. Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid Dianhydride, 4,4'-oxydiphthalic dianhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic dianhydride , Naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride , Naphthalene-1,4,5,8-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5 6,7-Hexahydronaphthalene 1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride,

2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, , 4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride, 2,2 ′, 3 , 3′-diphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyltetracarboxylic dianhydride, 3,3 ″, 4,4 ″ -p-terphenyltetracarboxylic dianhydride 2,3,3 ", 4" -p-terphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, 2,2-bis (3 4-dicarboxyphenyl) -propane dianhydride, bis (2,3 Dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane Dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane Anhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride,

Perylene-2,3,8,9-tetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride Perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride , Phenanthrene-1,2,9,10-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic acid And dianhydrides, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, and the like. Absent. Moreover, in using these, it may be individual or a mixture of 2 or more types.

In the synthesis of the polyamic acid ester, usually, a method of subjecting a tetracarboxylic acid diester obtained by performing an esterification reaction of a tetracarboxylic dianhydride described later to a condensation reaction with a diamine as it is can be preferably used.
In the polyamic acid ester, Y and Y ′ groups in the repeating unit are derived from an aromatic diamine used as a raw material. Examples of the aromatic diamine include 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-diethyl-4,4′-diaminodiphenylmethane, and 3,3′-dipropyl-4,4 ′. -Diaminodiphenylmethane, 3,3'-diisopropyl-4,4'-diaminodiphenylmethane, etc. can be mentioned.

The alcohols used in the esterification reaction of the tetracarboxylic dianhydride are alcohols having an olefinic double bond. Specifically, 2-methacryloyloxyethyl alcohol, 2-acryloyloxyethyl alcohol, 1-acryloyloxy-2-propyl alcohol, 2-methacrylamide ethyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl Examples thereof include vinyl ketone and 2-hydroxyethyl methacrylate. These alcohols can be used alone or in combination of two or more.
Further, as described in JP-A-06-080776, a part of the alcohol having an olefinic double bond, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol and allyl alcohol, is mixed. It can also be used.
Theoretically, the amount of alcohol used for esterification of tetracarboxylic dianhydride is 1.0 equivalent per 1.0 equivalent of tetracarboxylic dianhydride. When tetracarboxylic acid diester is synthesized using alcohol so that 1.01 to 1.10 equivalent per 1.0 equivalent of the product, the storage stability of the finally obtained photosensitive polyamic acid ester composition is improved. Therefore, it is preferable.

In the composition of the present invention, i-line permeability, high heat resistance and high chemical resistance, and other performances are achieved by the polyamic acid ester in which the specific tetracarboxylic dianhydride and the specific diamine described above are combined. Can be balanced.
The molar ratio of the tetracarboxylic acid diester and the diamine used for the synthesis of the polyamic acid ester is preferably around 1.0, but in the range of 0.7 to 1.3 depending on the molecular weight of the target polyamic acid ester. Can be used.
As a specific method for synthesizing the polyamic acid ester used in the present invention, a conventionally known method can be employed. About this, the method shown by the international publication 00/43439 pamphlet can be used, for example.
The weight average molecular weight of the polyamic acid ester used in the present invention is preferably 8000 to 150,000, and more preferably 9000 to 50000. When the weight average molecular weight is 8000 or more, the mechanical properties are improved, and when it is 150,000 or less, the dispersibility in the developer is improved, and the resolution performance of the relief pattern is improved.

（式中、Ｒ₁ 、Ｒ₂ 、Ｒ₃ 、Ｒ₄ 、Ｒ₆ は１価の有機基であり、Ｒ₅ は２価の有機基である。なお、式中の芳香族環上の水素原子は、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ−ブチル基、フッ素原子、及びトリフルオロメチル基からなる群の中から選ばれる、少なくとも１個の基で置換されていても良い。） Moreover, as a component which improves heat resistance and chemical resistance, 0 to 50% of tetracarboxylic dianhydride which is a raw material of the polyamic acid ester used in the present invention is represented by the following structural formula (3). The dicarboxylic acid compound having a divalent organic group may be used for copolymerization.

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₆ are monovalent organic groups, and R ₅ is a divalent organic group. In addition, a hydrogen atom on the aromatic ring in the formula Is substituted with at least one group selected from the group consisting of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a fluorine atom, and a trifluoromethyl group. May be.)

The dicarboxylic acid compound having a divalent organic group represented by the above formula (3) is specifically a 5-aminoisophthalic acid derivative. Derivatives can be divided into the following three systems.
As a derivative of system 1, by reacting an amino group of 5-aminoisophthalic acid with an acid chloride, acid anhydride, isocyanate, or epoxy compound having a thermal crosslinking group, the amino group of 5-aminoisophthalic acid is converted into an amino group. It is a compound into which a thermal crosslinking group has been introduced.
As the thermal crosslinking group, those that cause a self-crosslinking reaction in the range of 150 to 400 ° C. are desirable. Norbornene group, glycidyl group, cyclohexene group, ethynyl group, allyl group, aldehyde group, benzocyclobutene group, furyl group, furfuryl Preferred examples include a group, dimethoxydimethylamino group, dihydroxydimethylamino group, alkynyl group, alkenyl group, oxetane group, methacrylate group, acrylate group, cyano group and thiophene group.

  Specific examples of the acid chloride, acid anhydride, isocyanate, or epoxy compound having the thermal crosslinking group include 5-norbornene-2,3-dicarboxylic acid anhydride, exo-3,6-epoxy-1,2. , 3,6-tetrahydrophthalic anhydride, 3-ethynyl-1,2-phthalic anhydride, 4-ethynyl-1,2-phthalic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride 1-cyclohexene-1,2-dicarboxylic anhydride, maleic anhydride, 3-cyclohexene-1-carboxylic acid chloride, anhydrous endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride Acid, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, 2-furancarboxylic acid chloride, Rotonic acid chloride, cinnamic acid chloride, methacrylic acid chloride, acrylic acid chloride, propiolic acid chloride, tetrolic acid chloride, citraconic anhydride, itaconic anhydride, thiophene 2-acetyl chloride, isocyanate ethyl methacrylate, allyl succinic anhydride, glycidyl Examples include methacrylate and allyl glycidyl ether.

The derivative of the system 2 is a compound in which the amino group of 5-aminoisophthalic acid is protected with a urethane-type protecting group, an acyl-type protecting group, an alkyl-type protecting group, a silicon-type protecting group, a urea-type protecting group, or the like. This protecting group is selected so that the polybenzoxazole precursor is eliminated in the step of ring closure by heating, and the amino group is regenerated. The regenerated amino group causes a cross-linking reaction with a part of the polymer main chain or the terminal part.
Examples of urethane-type protecting groups include benzyloxycarbonyl group, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, isobutyloxycarbonyl group, t-butyloxycarbonyl group, p-nitrobenzyloxycarbonyl group, p-methoxy. Examples include a benzyloxycarbonyl group, an isobornylbenzyloxycarbonyl group, and a p-biphenylisopropylbenzyloxycarbonyl group.

  Specific examples of compounds used to protect the amino group of 5-aminoisophthalic acid with a urethane-type protecting group include chlorocarbonic acid methyl ester, chlorocarbonic acid ethyl ester, chlorocarbonic acid n-propyl ester, chlorocarbonic acid isopropyl ester, and chlorocarbonic acid isobutyl. Ester, chlorocarbonic acid 2-ethoxy ester, chlorocarbonic acid-sec-butyl ester, chlorocarbonic acid benzyl ester, chlorocarbonic acid 2-ethylhexyl ester, chlorocarbonic acid allyl ester, chlorocarbonic acid phenyl ester, chlorocarbonic acid 2,2,2-trichloroethyl ester Chlorocarbonic acid-2-butoxyethyl ester, chlorocarbonic acid-p-nitrobenzyl ester, chlorocarbonic acid-p-methoxybenzyl ester, chlorocarbonic acid isobornylbenzyl ester, chlorocarbonic acid-p-biphenylisopro Chlorocarbonates such as rubenzyl ester, 2-t-butyloxycarbonyl-oxyimino-2-phenylacetonitrile, St-butyloxycarbonyl-4,6-dimethyl-thiopyrimidine, di-t-butyl-dicarbonate, etc. Is mentioned.

Examples of acyl-type protecting groups include formyl group, phthaloyl group, dithiasuccinoyl group, tosyl group, mesyl group, o-nitrophenylsulfenyl group, o-nitropyridinesulfenyl group, and diphenylphosphinyl group. . Examples of the acyl-type protecting reagent include N-ethoxycarbonylphthalimide, ethyldithiocarbonyl chloride, formic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride, methanesulfonic acid chloride, acetyl chloride and the like.
Examples of the alkyl-type protecting group include a triphenylmethyl group and a 2-benzoyl-1-methylvinyl group. Examples of the alkyl type protecting reagent include trityl chloride. Examples of the silicon-type protecting group include trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, and t-butyldiphenylsilyl group. Silicon type protective reagents include trimethylchlorosilane, hexamethyldisilazane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (dimethylamino) trimethylsilane , Trimethylsilyldiphenylurea, bis (trimethylsilyl) urea and the like.

As the urea-type protecting group, 5-aminoisophthalic acid and various monoisocyanate compounds may be reacted. Examples of the monoisocyanate compound include isocyanic acid phenyl ester, isocyanic acid n-butyl ester, isocyanic acid n-octadecyl ester, and isocyanic acid o-tolyl ester. Examples of the monoisocyanate compound include phenyl isocyanate, n-butyl isocyanate, n-octadecyl isocyanate, and o-tolyl isocyanate.
The derivative of the system 3 is a compound obtained by reacting the amino group of 5-aminoisophthalic acid with a dicarboxylic acid anhydride. Examples of the dicarboxylic acid anhydride include 1,2-phthalic acid anhydride, cis-1,2-cyclohexanedicarboxylic acid anhydride, glutaric acid anhydride, and the like.

（式中、Ｘ”は４価の芳香族基である。ただし、ピロメリット酸二無水物、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物は除く。Ｒ”はオレフィン性二重結合を有する１価の基である。Ｙ”は２価の芳香族基である。） In addition, the photosensitive polyamic acid ester composition of the present invention is a polyamide represented by the following general formula (4) in order to further improve the adhesion to the polyamic acid ester (a) described in the general formula (1). You may mix and use acid ester (b). The addition amount of the polyamic acid ester (b) is mixed so that the total amount with the polyamic acid ester (a) is 100 parts by weight, and the weight ratio is (a) :( b) = 100: 0 to 50:50. Preferably there is.

(In the formula, X ″ is a tetravalent aromatic group, provided that pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, Excluding 4′-biphenyltetracarboxylic dianhydride. R ″ is a monovalent group having an olefinic double bond. Y ″ is a divalent aromatic group.)

  In the polyamic acid ester (b), X ″ in the repeating unit is derived from a tetracarboxylic dianhydride used as a raw material. Specific examples of preferred aromatic tetracarboxylic dianhydrides that can be used as X ″ Examples include 4,4′-oxydiphthalic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis ( 3,4-dicarboxyphenyl) sulfide dianhydride, bis (4- (4-aminophenoxy) phenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4 -Dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-di Ruboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3 , 4-Dicarboxyphenoxy) benzene dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, 2,2-bis [(3,4-dicarboxyphenoxy) phenyl] propane And dianhydrides, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 1,4,5,8-naphthalenetetracarboxylic dianhydride. These aromatic tetracarboxylic dianhydrides can be used alone or in combination of two or more.

  In the polyamic acid ester (b), R ″ in the repeating unit is derived from alcohols used for the esterification reaction of the tetracarboxylic dianhydride. Alcohols used for the esterification reaction of the tetracarboxylic dianhydride Are alcohols having an olefinic double bond, specifically 2-methacryloyloxyethyl alcohol, 2-acryloyloxyethyl alcohol, 1-acryloyloxy-2-propyl alcohol, 2-methacrylamide ethyl alcohol. , 2-acrylamidoethyl alcohol, methylol vinyl ketone, 2-hydroxyethyl vinyl ketone, 2-hydroxyethyl methacrylate, etc. These alcohols can be used alone or in combination of two or more. .

Further, as described in JP-A-06-080776, a part of the alcohol having an olefinic double bond, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol and allyl alcohol, is mixed. It can also be used.
Theoretically, the amount of alcohol used for esterification of tetracarboxylic dianhydride is 1.0 equivalent per 1.0 equivalent of tetracarboxylic dianhydride. When tetracarboxylic acid diester is synthesized using alcohol so that 1.01 to 1.10 equivalent per 1.0 equivalent of the product, the storage stability of the finally obtained photosensitive polyamic acid ester composition is improved. Therefore, it is preferable.

  In the polyamic acid ester (b), Y ″ in the repeating unit is derived from an aromatic diamine used as a raw material. Specific examples of preferred aromatic diamines that can be used as Y ″ include paraphenylenediamine. , Metaphenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-methylenebis (2-methylaniline), 4,4′-diaminodiphenyl sulfide, 4,4′-diaminobenzophenone, 3,4′-diaminodiphenyl ether 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfoxide, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′- Dimethyl-4,4′-diaminobiphenyl, 3,3′-dimeth Si-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diaminobiphenyl, 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, 1,4-bis (4-aminophenyl) benzene, 9,10 -Bis (4-aminophenyl) anthracene, 1,1,1,3,3,3-hexafluoro-2,2-bis (4-aminophenyl) propane 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2, 2-bis (3-amino-4-methylphenyl) propane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, or part of a hydrogen atom directly bonded to the aromatic ring of these aromatic diamines In which is substituted with a group selected from the group consisting of a methyl group, an ethyl group, and a halogen group.

(B) Photoinitiator Examples of the photoinitiator that is a component of the photosensitive polyamic acid ester composition of the present invention include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenylketone, and dibenzyl. Ketones, benzophenone derivatives such as fluorenone, 2,2′-diethoxyacetophenone, and acetophenone derivatives such as 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, thioxanthone, 2-methylthioxanthone, 2- Thioxanthone derivatives such as isopropylthioxanthone and diethylthioxanthone, benzyl derivatives such as benzyl, benzyldimethyl ketal and benzyl-β-methoxyethyl acetal, benzoin derivatives such as benzoin methyl ether, 2 Azides such as 6-di (4′-diazidobenzal) -4-methylcyclohexanone and 2,6′-di (4′-diazidobenzal) cyclohexanone, 1-phenyl-1,2-butanedione-2- (o-methoxy) Carbonyl) oxime, 1-phenylpropanedione-2- (o-methoxycarbonyl) oxime, 1-phenylpropanedione-2- (o-ethoxycarbonyl) oxime, 1-phenylpropanedione-2- (o-benzoyl) oxime Oximes such as 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime and 1-phenyl-3-ethoxypropanetrione-2- (o-benzoyl) oxime, N such as N-phenylglycine -Peroxides such as arylglycines and benzoyl peroxide, Aromatic biimidazoles, although such titanocenes are used, the oximes are preferred in view of curability and photosensitivity of a thick film.
As for the addition amount of these photoinitiators, 1-15 mass parts is preferable with respect to 100 mass parts of (A) polyamic-acid ester. Addition of 1 part by mass or more of the initiator to 100 parts by mass of the polyamic acid ester provides excellent photosensitivity, and addition of 15 parts by mass or less provides excellent thick film i-line curability.

(C) Solvent As the solvent that is a component of the photosensitive polyamic acid ester composition of the present invention, a polar organic solvent is preferably used from the viewpoint of solubility in the components (A) and (B). Specifically, N, N-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone , Tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone and the like, and these can be used alone or in combination of two or more.
These solvents can be used in the range of 30 to 600 parts by mass with respect to 100 parts by mass of the (A) polyamic acid ester, depending on the coating film thickness and viscosity.
Furthermore, in order to improve the storage stability of the polyamic acid ester composition of the present invention, it is preferable that an alcohol be included in the organic solvent used as the solvent.

The alcohol that can be used is not particularly limited as long as it has an alcoholic hydroxyl group in the molecule. Specific examples thereof include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butyl. Lactic acid esters such as alcohol, isobutyl alcohol, tert-butyl alcohol, ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, Propylene glycol monoalkyl ethers such as propylene glycol-1- (n-propyl) ether and propylene glycol-2- (n-propyl) ether, ethylene glycol methyl ether, ethylene glycol Le ethyl ether, mono-alcohols such as ethylene glycol -n- propyl ether, 2-hydroxyisobutyric acid esters, ethylene glycol, di alcohols such as propylene glycol, and the like. Among these, lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyric acid esters, and ethyl alcohol are preferable. Particularly, ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, propylene Glycol-1- (n-propyl) ether is more preferred.
The alcohol content in the total solvent is preferably 5 to 50% by weight, more preferably 10 to 30% by weight. When the alcohol content is 5% by weight or more, the storage stability of the polyamic acid ester composition is improved. Moreover, when it is 50 weight% or less, the solubility of the polyamic acid ester which is (A) component becomes favorable.

(D) Other components A sensitizer may be added to the photosensitive polyamic acid ester composition of the present invention in order to further improve the photosensitivity. Examples of the sensitizer for improving the photosensitivity include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzal) cyclopentane, 2,6-bis ( 4'-diethylaminobenzal) cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone P-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p -Dimethylaminophenylvinylene) isonaphthothiazole, 1, -Bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethyl Aminocoumarin, 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-dimethylaminostyryl) naphtho (1,2-d) thi Examples include azole, 2- (p-dimethylaminobenzoyl) styrene, benzotriazole, 5-methylbenzotriazole, and 5-phenyltetrazole. Among these, it is preferable to use a combination of a compound having a mercapto group and a compound having a dialkylaminophenyl group in terms of photosensitivity. These can be used alone or in combination of 2 to 5 kinds.
The sensitizer for improving the photosensitivity is preferably used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the (A) polyamic acid ester.

In addition, an adhesion aid can be added to the photosensitive polyamic acid ester composition of the present invention in order to improve adhesion to the substrate. Adhesion 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-1, 4-bis (N- [3-triet Sisilyl] propylamide) -2,5-dicarboxylic acid, 3- (triethoxysilyl) propyl succinic anhydride, silane coupling agents such as N-phenylaminopropyltrimethoxysilane, and aluminum tris (ethylacetoacetate), Examples thereof include aluminum adhesion assistants such as aluminum tris (acetylacetonate) and ethyl acetoacetate aluminum diisopropylate.
In these, it is more preferable to use a silane coupling agent from the point of adhesive force. The addition amount of the adhesion assistant is preferably in the range of 0.5 to 10 parts by mass with respect to (A) 100 parts by mass of the polyamic acid ester.

In addition, a thermal polymerization inhibitor can be added to the photosensitive polyamic acid ester composition of the present invention in order to improve the viscosity of the composition solution during storage and the stability of photosensitivity. Examples of thermal polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6 -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 and the like are used.
As a quantity of the thermal-polymerization inhibitor added to a photosensitive polyamic-acid ester composition, the range of 0.005-5 mass parts is preferable with respect to 100 mass parts of (A) polyamic-acid ester.
In the photosensitive polyamic acid ester composition of the present invention, an organic titanium compound can be used as a component for improving heat resistance and chemical resistance. The usable organic titanium compound is not particularly limited as long as the organic chemical substance is bonded to the titanium atom through a covalent bond or an ionic bond.

Specific examples of organotitanium compounds that can be used are first titanocenes. As the titanocene, pentamethylcyclopentadienyl titanium trimethoxide and the like are used. In this case, if titanocenes that function as a photoinitiator such as bis (2,6-difluoro-3- (1-hydropyrrol-1-yl) phenyl) titanocene are used, there are other cases that may be used in the present invention. An organic titanium compound that does not function as a photoinitiator may be more preferable because a good pattern may be difficult to obtain due to interference with the photoinitiator.
Another specific example of the organic titanium compound that can be used in the present invention is a titanium chelate. In the present invention, among the titanium chelates, those having two or more alkoxy groups are more preferable because the stability of the composition and a good pattern can be obtained. Specific preferred examples include titanium bis (triethanol Amine) diisopropoxide, titanium di (n-butoxide) (bis-2,4-pentanedionate), titanium diisopropoxide (bis-2,4-pentanedionate), titanium diisopropoxide bis ( Tetramethylheptanedionate), titanium diisopropoxide bis (ethylacetoacetate) and the like.

The present invention also includes titanium tetra (n-butoxide), titanium tetraethoxide, titanium tetra (2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium. Tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra (n-nonyloxide), titanium tetra (n-propoxide), titanium tetrastearyloxide, titanium tetrakis (bis-2,2- (allyloxymethyl) butoxide), Monoalkoxides such as tetraalkoxides such as titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzenesulfonate) isopropoxide Sides, Titanium oxide bis (pentanedionate), Titanium oxide bis (tetramethylheptanedionate), Titanium oxides such as phthalocyanine titanium oxide, Tetraacetylacetonates such as titanium tetraacetylacetonate, Isopropyltridodecylbenzenesulfonyl Titanate coupling agents such as titanate can also be used.
The addition amount of these organic titanium compounds is preferably 0.3 to 10 parts by mass, more preferably 0.5 to 2 parts by mass with respect to 100 parts by mass of the (A) polyamic acid ester. When the addition amount is 0.3 parts by mass or more, desired heat resistance and chemical resistance are exhibited, and when it is 10 parts by mass or less, the storage stability is excellent.

  A reactive monomer can also be added to the photosensitive polyamic acid ester composition of the present invention. Although it does not specifically limit as a reactive monomer, The thing which carries out radical polymerization reaction by the effect | action of a photoradical generator, or the thing which carries out ring-opening polymerization reaction by the action of a photoacid generator or a photobase generator can be selected. Although it does not specifically limit as a reactive monomer which carries out radical polymerization reaction, The mono- or diacrylate and methacrylate of ethylene glycol or polyethyleneglycol, including diethylene glycol and tetraethyleneglycol dimethacrylate, the mono- or diacrylate of propylene glycol or polypropylene glycol, or Diacrylate and methacrylate, glycerol mono-, di- or triacrylate and methacrylate, cyclohexane diacrylate and dimethacrylate, diacrylate and dimethacrylate of 1,4-butanediol, diacrylate and dimethacrylate of 1,6-hexanediol, neo Pentyl glycol diacrylate and dimethacrylate, bisphenol A Or diacrylate and methacrylate, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and derivatives thereof, methacrylamide and derivatives thereof, trimethylolpropane triacrylate and methacrylate, glycerol di or triacrylate and methacrylate, pentaerythritol di, Mention may be made of compounds such as tri- or tetraacrylates and methacrylates, and ethylene oxide or propylene oxide adducts of these compounds.

<Method for forming cured relief pattern>
As one aspect of the method for forming a cured relief pattern comprising a photosensitive polyimide resin using the photosensitive polyamic acid ester composition, the following steps are preferred.
(A) The process of forming a coating film on this base material by apply | coating the photosensitive polyamic-acid ester composition to a base material, and drying.
(B) A step of irradiating the coating film with ultraviolet rays through a photomask or reticle having a pattern or directly.
(C) The process which removes the part which was not exposed of this coating film by developing with a developing solution, and forms a relief pattern on this board | substrate by this.
(D) A step of imidizing the polyamic acid ester in the relief pattern by heat-curing the relief pattern, thereby forming a cured relief pattern made of polyimide resin on the substrate.

Examples of the substrate that can be used in the method of forming a cured relief pattern include a silicon wafer, metal, glass, semiconductor, metal oxide insulating film, silicon nitride, and the like, and a silicon wafer is preferably used.
As a method for coating the photosensitive polyamic acid ester composition used in the present invention on a substrate, methods conventionally used for coating photosensitive polyamic acid ester compositions, such as spin coaters, bar coaters, blades, etc. A coating method using a coater, curtain coater, screen printer, or the like, a spray coating method using a spray coater, or the like can be used.
As a method for drying the coating film, methods such as air drying, heat drying with an oven or hot plate, and vacuum drying are used. Moreover, it is desirable that the coating film be dried under conditions such that imidation of the polyamic acid ester in the photosensitive polyamic acid ester composition does not occur. Specifically, when performing air drying or heat drying, it can be performed at 20 ° C. to 140 ° C. for 1 minute to 1 hour.

The coating film thus obtained is exposed with an ultraviolet light source or the like through a photomask or reticle having a pattern, using an exposure apparatus such as a contact aligner, mirror projection, or stepper, and then developed.
The developer used for development is preferably a good solvent for the polyamic acid ester composition or a combination of the good solvent and the poor solvent. Good solvents include N-methylpyrrolidone (hereinafter also referred to as “NMP”), N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone. As the poor solvent, toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water and the like are used. When a good solvent and a poor solvent are mixed and used, the ratio of the poor solvent to the good solvent is adjusted depending on the solubility of the polymer. Moreover, several types of solvents can be used in combination.

As a method used for development, an arbitrary method can be selected and used from conventionally known photoresist development methods such as a rotary spray method, a paddle method, and an immersion method involving ultrasonic treatment.
The polyamic acid ester pattern obtained as described above is converted into a cured relief pattern made of polyimide resin by heating to disperse the photosensitive component and imidize it. Various methods such as a method using a hot plate, a method using an oven, and a method using a temperature rising oven capable of setting a temperature program can be selected as the method for heat curing. Heating can be performed at 280 ° C. to 450 ° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas for heat curing, and an inert gas such as nitrogen or argon may be used.

<Method for producing laminate>
As one aspect of the method for producing a laminate comprising a cured relief pattern layer made of a polyimide resin and a metal layer using the above-described photosensitive polyamic acid ester composition, the following steps are preferable.
Following the step of forming the cured relief pattern on the substrate by the above-described method of forming a cured relief pattern, the surface of the layer is subjected to dry etching treatment such as ashing or plasma etching.
The dry etching treatment is preferably performed using a gas such as oxygen, argon, or carbon tetrafluoride under conditions of a pressure of 1 to 100 Pa and a time of 1 to 30 minutes.
As described above, a bump or rewiring metal layer (a metal layer such as titanium, aluminum, or copper) is further in contact with the cured relief pattern made of a polyimide resin obtained on the base material. The laminated body of this invention can be manufactured by providing by thin film preparation methods, such as sputtering. And the semiconductor device which has at least 1 sort (s) of metal layer selected from the group which consists of titanium and aluminum on a polyimide resin layer is manufactured by combining the manufacturing method of this laminated body with the manufacturing method of a well-known semiconductor device. be able to.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.
In Examples, Comparative Examples and Reference Examples, the physical properties of the photosensitive polyamic acid ester composition were measured and evaluated according to the following methods.
(1) Weight average molecular weight The weight average molecular weight (Mw) of each polyamic acid ester was measured by the gel permeation chromatography method (standard polystyrene conversion).
The analysis conditions for GPC are described below.
Column: Showa Denko Co., Ltd. Trade name: Shodex 805/804/803 in series Separation: Tetrahydrofuran 40 ° C
Flow rate: 1.0 ml / min Detector: Showa Denko Co., Ltd. Trade name Shodex RI SE-61
(2) Measurement of glass transition temperature (Tg) of polyimide coating film On a 5-inch silicon wafer (produced by Fujimi Electronics Co., Ltd., Japan) having a thickness of 625 μm ± 25 μm as a substrate, the film thickness after curing is about 10 μm. The photosensitive polyamic acid ester composition was spin-coated so as to be, and then heated at 350 ° C. for 2 hours in a nitrogen atmosphere to obtain a thermosetting polyimide coating film. The obtained polyimide coating film was peeled off from the silicon wafer to obtain a polyimide tape.
The obtained polyimide tape was measured with a thermomechanical test apparatus (manufactured by Shimadzu Corp .: TMA-50) at a load of 200 g / mm ² and a heating rate of 10 ° C./min, 20 to 500 ° C. The tangential intersection of the thermal yield points of the polyimide tape in the measurement chart with the amount on the vertical axis was defined as Tg.

(3) Preparation method of cured relief pattern and evaluation of resolution The photosensitive polyamic acid ester composition was spin-coated on a 5-inch silicon wafer and dried to form a 10 μm thick coating film. This coating film was irradiated with energy of 300 mJ / cm ² using an i-line stepper NSR1755i7B (Nikon Corporation, Japan) using a reticle with a test pattern. Subsequently, the coating film formed on the wafer is spray-developed with a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd.) using cyclopentanone as a developer, and rinsed with propylene glycol methyl ether acetate. Thus, a cured relief pattern was obtained.
The wafer on which the relief pattern was formed was heat-treated in a nitrogen atmosphere at 200 ° C. for 1 hour and subsequently at 350 ° C. for 2 hours using a temperature rising programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg, Japan). As a result, a cured relief pattern made of a polyimide resin having a thickness of about 5 μm was obtained on the silicon wafer.
About the obtained hardening relief pattern, the pattern shape and the width | variety of the pattern part were observed under the optical microscope, and the resolution was calculated | required. Regarding the resolution, a pattern having a plurality of openings with different areas is formed by the above method by exposing through a reticle with a test pattern, and the area of the resulting polyimide resin pattern opening is the corresponding pattern reticle opening. If the area is ½ or more of the area, it is regarded as resolved, and the length of the opening side of the reticle corresponding to the resolved opening having the smallest area is defined as the resolution. A resolution of 10 μm or less was considered good.

(4) Evaluation of chemical resistance of cured relief pattern About the cured relief pattern obtained by (3) above, NMP (40-60%) / sulfolane (30-50%) / 1-amino-2-propanol (5 -15%) in a mixed solution (PRS-3000) at 85 ° C. for 1 hour, and immersed in a mixed solution having a weight ratio of tetramethylammonium hydroxide (TMAH) / dimethyl sulfoxide (DMSO) of 6/94 at 60 ° C. for 40 minutes. Then, the surface pattern was observed and a chemical resistance test was performed. If there was no dissolution of the pattern, peeling of the pattern, or cracking of the coating film, the test was accepted.
(5) Evaluation of metal adhesion of polyimide coating film On a 5-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., Japan) having a thickness of 625 μm ± 25 μm serving as a substrate, the film thickness after curing is about 10 μm. After spin-coating the photosensitive polyamic acid ester composition, it was heated at 350 ° C. for 2 hours in a nitrogen atmosphere to obtain a thermosetting polyimide coating film.

  Low pressure plasma treatment is performed on this polyimide coating using an ashing device (EXAM, manufactured by Shinko Seiki Co., Ltd.) under conditions of oxygen: carbon tetrafluoride flow rate of 40 ml / min: 1 ml / min, 50 Pa, 133 W. It was. The polyimide coating film was subjected to argon plasma etching under the conditions of an argon flow rate of 50 sccm, 1 Pa, and 400 W using a sputtering apparatus (L-430S-FH, manufactured by Anelva). Further, an Al or Ti film having a thickness of 200 nm was formed on the polyimide coating film using a sputtering apparatus (L-430S-FH, manufactured by Anelva). On this Al or Ti film, an epoxy adhesive (made by Showa Polymer Co., Ltd., Araldite Standard) was used to bond a pin having a diameter of 2 mm, and this was pulled using a tensile tester (quad group, Sebastian type 5). A peel test was performed. If the force required for peeling was 60 MPa or more, it was determined to be acceptable.

Reference Example 1 (Synthesis of polyamic acid ester A)
Pyromellitic dianhydride (PMDA) 87.2g was put into a 2 liter separable flask, 10-g 2-hydroxyethyl methacrylate (HEMA) and 400ml γ-butyrolactone were added and stirred at room temperature. While adding 81.5 g of pyridine, a reaction mixture was obtained. After completion of the exothermic reaction, the mixture was allowed to cool to room temperature and left for 16 hours.
Next, under ice cooling, a solution prepared by dissolving 165.1 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 3,3′-dimethyl-4,4. A suspension of 84.1 g of '-diaminodiphenylmethane in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. After further stirring for 2 hours at room temperature, 30 ml of ethyl alcohol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.
The obtained reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 liter of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate a polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer (polyamic acid ester A). The weight average molecular weight (Mw) of the polyamic acid ester A was 23000.

Reference Example 2 (Synthesis of polyamic acid ester B)
As tetracarboxylic acid, 117.7 g of 3,3′4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 84.1 g of 3,3′-dimethyl-4,4′-diaminodiphenylmethane were used. In the same manner as in Reference Example 1, the polyamic acid ester B was obtained. The weight average molecular weight (Mw) of the polyamic acid ester B was 26000.
Reference Example 3 (Synthesis of polyamic acid ester C)
62.0 g of 4,4′-oxydiphthalic dianhydride (ODPA) and 58.8 g of 3,3′4,4′-biphenyltetracarboxylic dianhydride (BPDA) were used as tetracarboxylic acids, and 3 , 3′-dimethyl-4,4′-diaminodiphenylmethane was reacted in the same manner as in Reference Example 1 to obtain polyamic acid ester C. The weight average molecular weight (Mw) of the polyamic acid ester C was 26000.

Reference Example 4 (Synthesis of polyamic acid ester D)
By using 87.2 g of pyromellitic dianhydride (PMDA) as the tetracarboxylic acid and 74.3 g of 4,4′-diaminodiphenyl ether (DADPE) as the diamine, the reaction is performed in the same manner as in Reference Example 1 described above. Thus, polyamic acid ester D was obtained. The weight average molecular weight (Mw) of the polyamic acid ester D was 28,000.
Reference Example 5 (Synthesis of polyamic acid ester E)
Using 44.1′-oxydiphthalic dianhydride (ODPA) 124.1 g as tetracarboxylic acid and 84.1 g 3,3′-dimethyl-4,4′-diaminodiphenylmethane as diamine, the above-mentioned Reference Example 1 To give a polyamic acid ester E. The weight average molecular weight (Mw) of the polyamic acid ester E was 25000.

Reference Example 6 (Synthesis of polyamic acid ester F)
Using 128.9 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) as tetracarboxylic acid and 94.5 g of 4,4′-methylenedi-2,6-xylidine as diamine, A polyamic acid ester F was obtained by reacting in the same manner as in Reference Example 1 described above. The weight average molecular weight (Mw) of the polyamic acid ester F was 27000.
Reference Example 7 (Synthesis of polyamic acid ester G)
Using 44.1'-oxydiphthalic dianhydride (ODPA) 124.1 g as the tetracarboxylic acid and 74.4 g 4,4'-diaminodiphenyl ether (DADPE) as the diamine, the same method as in Reference Example 1 above. To obtain a polyamic acid ester G. The weight average molecular weight (Mw) of the polyamic acid ester G was 18,000.

[Example 1]
Using the obtained polyamic acid ester A, a photosensitive polyamic acid ester composition was prepared by the following method, and the prepared composition was evaluated.
100 g of polyamic acid ester A, 4 g of diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime (photoinitiator), 4 g of tetraethylene glycol dimethacrylate, 2 g of 1-phenyl-5-mercaptotetrazole, 4 g of N-phenyldiethanolamine, N -It was dissolved in a mixed solvent consisting of 80 g of NMP and 20 g of ethyl lactate together with 3 g of [3- (triethoxysilyl) propyl] phthalamic acid and 0.02 g of 2-nitroso-1-naphthol. The viscosity of the obtained solution was adjusted to about 75 poise by further adding a small amount of the mixed solvent to obtain a photosensitive polyamic acid ester composition.
The Tg of the polyimide coating film obtained from the composition was 350 ° C. The resolution of the cured relief pattern was 8 μm. Further, in the chemical resistance test using PRS-3000 and TMAH / DMSO, pattern dissolution, pattern peeling, and cracks in the coating film were not observed.
When the metal adhesion of the polyimide coating film obtained from the composition was measured by the above method, both Al and Ti were 60 MPa or more.

[Example 2]
A photosensitive polyamic acid ester composition was prepared and evaluated in the same manner as in Example 1 except that the polyamic acid ester B was used instead of the polyamic acid ester A.
The Tg of the polyimide coating film obtained from the composition was 300 ° C. The resolution of the cured relief pattern was 7 μm. Further, in the chemical resistance test using PRS-3000 and TMAH / DMSO, pattern dissolution, pattern peeling, and cracks in the coating film were not observed.
When the metal adhesion of the polyimide coating film obtained from the composition was measured by the above method, both Al and Ti were 60 MPa or more.

[Example 3]
A photosensitive polyamic acid ester composition was prepared and evaluated in the same manner as in Example 1 except that the polyamic acid ester C was used instead of the polyamic acid ester A.
The Tg of the polyimide coating film obtained from the composition was 285 ° C. The resolution of the cured relief pattern was 7 μm. Further, in the chemical resistance test using PRS-3000 and TMAH / DMSO, pattern dissolution, pattern peeling, and cracks in the coating film were not observed.
When the metal adhesion of the polyimide coating film obtained from the composition was measured by the above method, both Al and Ti were 60 MPa or more.

[Comparative Example 1]
A photosensitive polyamic acid ester composition was prepared and evaluated in the same manner as in Example 1 except that the polyamic acid ester D was used instead of the polyamic acid ester A.
The Tg of the polyimide coating film obtained from the composition was 360 ° C. Further, in the chemical resistance test using PRS-3000 and TMAH / DMSO, pattern dissolution, pattern peeling, and cracks in the coating film were not observed. However, the relief pattern was not resolved in the i-line stepper exposure.
When the metal adhesion of the polyimide coating film obtained from the composition was measured by the above method, both Al and Ti were 60 MPa or more.

[Comparative Example 2]
A photosensitive polyamic acid ester composition was prepared and evaluated in the same manner as in Example 1 except that the polyamic acid ester E was used instead of the polyamic acid ester A.
The Tg of the polyimide coating film obtained from the composition was 275 ° C. The resolution of the cured relief pattern was 7 μm. However, dissolution of the pattern was observed in the chemical resistance test using PRS-3000 and TMAH / DMSO.
When the metal adhesion of the polyimide coating film obtained from the composition was measured by the above method, both Al and Ti were 60 MPa or more.

[Comparative Example 3]
A photosensitive polyamic acid ester composition was prepared and evaluated in the same manner as in Example 1 except that the polyamic acid ester F was used instead of the polyamic acid ester A.
The Tg of the polyimide coating film obtained from the composition was 285 ° C. The resolution of the cured relief pattern was 6 μm. However, dissolution was observed in the pattern in the chemical resistance test using PRS-3000 and TMAH / DMSO.
When the metal adhesion of the polyimide coating film obtained from the composition was measured by the above method, both Al and Ti were 60 MPa or more.

[Comparative Example 4]
A photosensitive polyamic acid ester composition was prepared and evaluated in the same manner as in Example 1 except that the polyamic acid ester G was used in place of the polyamic acid ester A, and 10 g of Nikalac MX-270 manufactured by Sanwa Chemical was added as a crosslinking agent. Went.
The Tg of the polyimide coating film obtained from the composition was 270 ° C. The resolution of the cured relief pattern was 8 μm. Further, in the chemical resistance test using PRS-3000 and TMAH / DMSO, pattern dissolution, pattern peeling, and cracks in the coating film were not observed.
When the metal adhesion of the polyimide coating film obtained from the composition was measured by the above method, it was 25 MPa for Al and 34 MPa for Ti.

  The composition of the present invention can be suitably used in the field of photosensitive materials useful for the production of electrical / electronic materials such as semiconductor devices and multilayer wiring boards. More specifically, the composition of the present invention can be suitably used as a polyamic acid ester composition capable of i-line exposure and giving a polyimide pattern having high heat resistance and chemical resistance.

Claims (3)

(A) 1 to 15 parts by mass of a photoinitiator and (C) 30 to 600 parts by mass of a solvent with respect to 100 parts by mass of a polyamic acid ester composed of a repeating unit represented by the following general formula (1) A photosensitive polyamic acid ester composition comprising:

[Wherein X is a tetravalent aromatic group containing one benzene ring, or a tetravalent aromatic group in which two benzene rings are single-bonded, and X ′ is one or two benzene rings. Is a tetravalent aromatic group. It is 0.5 <= m / (m + n) <= 1.0. R and R ′ are each independently a monovalent group having an olefinic double bond and may be the same or different. Y and Y ′ are divalent aromatic groups represented by the following general formula (2), which may be the same or different.

(In the formula, A is a divalent aliphatic group having 1 to 4 carbon atoms, and B is a monovalent aliphatic group having 1 to 4 carbon atoms.)]   It has the layer which consists of a relief pattern formed by hardening | curing the photosensitive polyamic-acid ester composition of Claim 1, and at least 1 sort (s) of metal layer selected from the group which consists of titanium and aluminum which contact | connects this layer, It is characterized by the above-mentioned. Laminated body.   A process of forming a coating film on a substrate by applying the photosensitive polyamic acid ester composition according to claim 1 to the substrate and drying, a photomask having a pattern, or directly A step of irradiating the film with ultraviolet rays, a step of removing the unexposed portion of the coating film by developing with a developer to form a relief pattern on the substrate, and a polyimide resin by heating the relief pattern Forming a layer comprising a cured relief pattern comprising: a step of dry etching the surface of the layer with at least one gas selected from argon, oxygen, and carbon tetrafluoride; and A step of forming at least one metal layer selected from the group consisting of titanium and aluminum in contact with the layer;