JP2010113349A - Photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which is excellent in resolution and adhesion, can be developed with an alkaline aqueous solution, and makes stripped chips soluble in a stripping step. <P>SOLUTION: The photosensitive resin composition comprises (a) 20-90 mass% of a thermoplastic copolymer comprising an α,β-unsaturated carboxyl group-containing monomer as a copolymerized component and having an acid equivalent of 100-600 and a weight average molecular weight of 5,000-500,000, (b) 5-75 mass% of an addition-polymerizable monomer having at least one terminal ethylenically unsaturated group, and (c) 0.01-30 mass% of a photopolymerization initiator comprising a triarylimidazolyl dimer. A photocured portion of the photosensitive resin composition is soluble in a release agent. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition that can be developed with an alkaline aqueous solution, a photosensitive resin laminate in which the photosensitive resin composition is laminated on a support, and a resist pattern on a substrate using the photosensitive resin laminate. And a use of the resist pattern. More specifically, the manufacture of printed wiring boards, the manufacture of flexible printed wiring boards, the manufacture of lead frames for mounting IC chips (hereinafter referred to as lead frames), metal foil precision processing such as metal mask manufacturing, and BGA (ball grid array) , Manufacturing of semiconductor packages such as CSP (chip size package), manufacture of tape substrates represented by TAB (Tape Automated Bonding) and COF (Chip On Film: a semiconductor IC mounted on a film-like fine wiring board), Sensation that gives a resist pattern suitable as a protective mask member when manufacturing a substrate by manufacturing semiconductor bumps, manufacturing members such as ITO electrodes, address electrodes, or electromagnetic wave shields in the field of flat panel displays, and sandblasting About RESIN composition.

  Conventionally, printed wiring boards are manufactured by a photolithography method. The photolithographic method is a method in which a photosensitive resin composition is applied onto a substrate, pattern exposure is performed to polymerize and cure the exposed portion of the photosensitive resin composition, and an unexposed portion is removed with a developer to form a resist on the substrate. A method of forming a conductor pattern on a substrate by forming a pattern, forming a conductor pattern by etching or plating, and then peeling and removing the resist pattern from the substrate.

  In the photolithography method described above, when a layer made of a photosensitive resin composition (hereinafter referred to as “photosensitive resin layer”) is laminated on a substrate, a photoresist solution is applied to the substrate and dried, or Any method of laminating a photosensitive resin laminate (hereinafter referred to as “dry film resist”) in which a support, a photosensitive resin layer, and, if necessary, a protective layer are sequentially laminated, is used. In the production of printed wiring boards, the latter dry film resist is often used.

  A method for producing a printed wiring board using the dry film resist will be briefly described below.

  First, when there is a protective layer such as a polyethylene film, it is peeled off from the photosensitive resin layer. Next, the photosensitive resin layer and the support are laminated on a substrate such as a copper clad laminate using a laminator so that the substrate, the photosensitive resin layer, and the support are in this order. Next, the exposed portion is polymerized and cured by exposing the photosensitive resin layer with ultraviolet rays emitted from an ultrahigh pressure mercury lamp through a photomask having a wiring pattern. Next, the support made of polyethylene terephthalate or the like is peeled off. Next, a non-exposed portion of the photosensitive resin layer is dissolved or dispersed and removed by a developing solution such as an aqueous solution having weak alkalinity to form a resist pattern on the substrate. Next, a known etching process or pattern plating process is performed using the formed resist pattern as a protective mask. Finally, the resist pattern is peeled from the substrate to produce a substrate having a conductor pattern, that is, a printed wiring board.

In recent years, as electronic devices are rapidly becoming highly functional and miniaturized, printed wiring boards are becoming more dense and multi-layered. In particular, there is an increasing demand for finer materials to cope with the narrow pitch of printed wiring boards, and there is an increasing demand for high resolution and high adhesion in dry film resists regardless of the field.
At the same time, it is necessary to be able to produce a large quantity at a low cost, and it is required to produce high-definition products with a high yield.

If the resolution and adhesion of the dry film is improved for the purpose of refinement, the resist pattern cannot be completely removed in the process of peeling the resist pattern from the substrate, causing a peeling residue on the substrate. Has been reported.
Generally, stripping solutions used in the process of stripping a resist pattern from a substrate include alkaline aqueous solutions such as sodium hydroxide and potassium hydroxide, organic solvents such as DMSO and DMF, and organic amine-based solutions such as alkanolamines. (Patent Document 1). Here, in order to improve the resolution and adhesion, if the resist pattern is increased in resistance to an alkaline developer (sodium carbonate aqueous solution), a side effect of peeling off occurs.
In the step of peeling the resist pattern from the substrate, (i) the peeling piece is too large and entangled with the roll of the peeling machine, the workability is remarkably reduced. (Ii) The peeled piece is too small and reattaches on the substrate, causing a decrease in yield. (Iii) There are many cases that cause various defects such as the peeling piece adhering to the nozzle and causing clogging of the nozzle, which causes a deterioration in yield and has been a big problem in the past. Here, the peeling piece refers to a resist pattern piece peeled from the substrate.

The trade-offs regarding dry film design and stripping solution solubility will be described in more detail below for each process.
In the wet etching method or the dry etching method (sand blast method or the like), resistance to the resist pattern etching solution or the dry etching material (abrasive material or the like) is required. This is an effective technique for improving resolution and adhesion at the same time, but as the crosslinking increases, the solubility in the stripping solution becomes poor, and stripping residues are likely to occur.
In the plating method, if a peeling residue is generated in the step of peeling the resist pattern after the plating step, the yield is greatly reduced. In order to solve this problem, if the resist pattern is designed to be soluble in the stripping solution, the resist pattern is less resistant to the plating solution, and a normal conductor pattern cannot be obtained.

  Since a dry film with a film thickness of 40-200um is generally used for semiconductor bump formation, enormous time is required for complete peeling in the process of swelling the resist pattern with a conventional stripping solution and stripping it from the substrate. Is necessary and productivity deteriorates. In addition, since various chemical solutions are used in the same manner as the plating step, it is very difficult to design solubilization in the stripping solution.

  Patent Documents 2 to 4 describe a method in which a peeling piece is dissolved in a peeling solution. However, although these have high solubility in the stripping solution of the resist pattern, at the same time, the resistance to the developer or the chemical solution is lost, and a product cannot be obtained with a high yield.

  For this reason, dry film resists that do not dissolve in the stripping solution are now widely used. However, high resolution and high adhesion are required to adapt to the recent narrower pitch of printed wiring boards. However, there has been a strong demand for a dry film resist that can dissolve the peeling piece and does not deteriorate the yield in the peeling process.

JP-A-2-221960 JP 9-265180 A JP 62-49355 A JP-A 62-43642

  The present invention is a photosensitive resin composition that has excellent resolution and adhesion, can be developed with an alkaline aqueous solution, and can dissolve a resist pattern piece peeled off from a substrate in the step of peeling the resist pattern from the substrate. It aims at providing the photosensitive resin laminated body using the photosensitive resin composition, the formation method of a resist pattern on a board | substrate using this photosensitive resin laminated body, and the use of this resist pattern. By making the peelable piece soluble, it is possible to solve various peeling troubles in the peeling step and greatly improve the yield.

  As a result of intensive studies to achieve the above object, the present inventor has found that the above object can be achieved by the following configuration of the present invention, and has completed the present invention.

｛式中、Ｒ_１及びＲ_２は、それぞれ独立に、Ｈ又はＣＨ_３であり、また、Ａ及びＢは、それぞれ独立に、炭素数が２〜４個のアルキレン基であり、ａ1、ａ2、ｂ1及びｂ2は、それぞれ、正の整数であり、かつ、ａ1、ａ2、ｂ1及びｂ2の合計は、２〜４０の整数であり、そして−（Ａ−Ｏ）−と−（Ｂ−Ｏ）−の繰り返し単位の配列は、ブロックでもランダムでよい。｝で表される化合物、又は、下記一般式（ＩＩ）：

｛式中、Ｒ_３及びＲ_４は、それぞれ独立に、Ｈ又はＣＨ_３であり、Ｄ及びＥは、それぞれ独立に、炭素数が２〜４個のアルキレン基であり、ａ3、ａ4、ｂ3及びｂ4は、それぞれ、正の整数であり、かつ、ａ3、ａ4、ｂ3及びｂ4の合計は、２〜４０であり、そして−（Ｄ−Ｏ）−と−（Ｅ−Ｏ）−の繰り返し単位の配列は、ブロックでもランダムでよい。｝で表される化合物からなる群より選ばれる少なくとも一種の化合物である、前記［１］又は［２］に記載の感光性樹脂組成物。 That is, the present invention is as follows.
[1]
(A) Thermoplastic copolymer containing an α, β-unsaturated carboxyl group-containing monomer as a copolymerization component and having an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000: 20 to 90 (B) Addition polymerizable monomer having at least one terminal ethylenically unsaturated group: 5 to 75% by mass, and (c) Photopolymerization initiator containing triarylimidazolyl dimer: 0.01 to 30 A photosensitive resin composition containing% by mass, wherein a photocured part of the photosensitive resin composition is soluble in a stripping solution.
[2]
(B) The photosensitive resin composition as described in [1] above, wherein the addition polymerizable monomer having at least one terminal ethylenically unsaturated group contains 3 to 40 ethylene oxide chains.
[3]
(B) An addition polymerizable monomer having at least one terminal ethylenically unsaturated group is represented by the following general formula (I):

{Wherein R ₁ and R ₂ are each independently H or CH ₃ , and A and B are each independently an alkylene group having 2 to 4 carbon atoms, a1, a2, b1 and b2 are each a positive integer, and the sum of a1, a2, b1, and b2 is an integer of 2 to 40, and-(A-O)-and-(B-O)- The arrangement of repeating units may be a block or random. } Or the following general formula (II):

{Wherein R ₃ and R ₄ are each independently H or CH ₃ , D and E are each independently an alkylene group having 2 to 4 carbon atoms, and a 3, a 4, b 3 and b4 is a positive integer, respectively, and the sum of a3, a4, b3 and b4 is 2 to 40, and-(DO)-and-(EO)- The arrangement can be random, even in blocks. } The photosensitive resin composition according to the above [1] or [2], which is at least one compound selected from the group consisting of compounds represented by:

｛式中、Ｘは、ハロゲン原子、水素原子、炭素数１〜２０のアルキル基、炭素数３〜１０のシクロアルキル基、アミノ基又は炭素数１〜２０のアルキル基で置換されてもよいフェニル基、ナフチル基を含むアリール基、アミノ基、メルカプト基、炭素数１〜１０のアルキルメルカプト基、アルキル基の炭素数が１〜１０のカルボキシアルキル基、炭素数１〜２０のアルコキシ基又は複素環であり、ｍ及びｎは、ｍが２以上の整数であり、ｎが０以上の整数であって、ｍ＋ｎ＝６となるように選ばれる整数であり、ｎが２以上の整数の時、２以上のＸは各々同一でも相違してもよい。｝で表される化合物をさらに含有する、前記［１］〜［３］のいずれか１に記載の感光性樹脂組成物。
［５］
（ａ）熱可塑性共重合体が、重合性不飽和基を少なくとも一個有する単量体を共重合成分として含む、前記［１］に記載の感光性樹脂組成物。 [4]
(D) General formula (III):

{In the formula, X is phenyl optionally substituted by a halogen atom, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an amino group, or an alkyl group having 1 to 20 carbon atoms. Group, aryl group including naphthyl group, amino group, mercapto group, alkyl mercapto group having 1 to 10 carbon atoms, carboxyalkyl group having 1 to 10 carbon atoms in alkyl group, alkoxy group having 1 to 20 carbon atoms or heterocyclic ring M and n are integers selected so that m is an integer of 2 or more, n is an integer of 0 or more, and m + n = 6, and when n is an integer of 2 or more, 2 The above Xs may be the same or different. } The photosensitive resin composition of any one of said [1]-[3] which further contains the compound represented by these.
[5]
(A) The photosensitive resin composition according to the above [1], wherein the thermoplastic copolymer contains a monomer having at least one polymerizable unsaturated group as a copolymerization component.

[6]
The photosensitive resin composition according to any one of [3] to [5], wherein the compound represented by the general formula (I) or the general formula (II) has a polyethyleneoxy group.
[7]
(B) The photosensitive resin composition of Claim 1 whose 70 mass% or more is acrylates in the said addition polymerizable monomer which has an at least 1 terminal ethylenically unsaturated group.
[8]
The photosensitive resin laminated body formed by laminating | stacking the photosensitive resin composition of any one of said [1]-[7] on a support body.
[9]
A resist pattern forming method comprising a lamination step of forming a photosensitive resin layer on the substrate using the photosensitive resin laminate described in [8] above, an exposure step, and a development step of removing unexposed portions in order.
[10]
In the exposure step, the resist pattern forming method according to [9], wherein direct exposure is performed by drawing.
[11]
The manufacturing method of a printed wiring board including the process of forming a resist pattern on a board | substrate by the method as described in said [9] or [10], and etching or plating this board | substrate.

[12]
A method for manufacturing a lead frame, comprising: forming a resist pattern on a substrate by the method according to [9] or [10] above; and etching the substrate.
[13]
A method for producing a concavo-convex substrate, comprising a step of forming a resist pattern on a substrate by the method according to [9] or [10], and sandblasting the substrate.
[14]
The manufacturing method of a semiconductor package including the process of forming a resist pattern on a board | substrate by the method as described in said [9] or [10], and etching or plating this board | substrate.
[15]
A method for producing a semiconductor bump, comprising a step of forming a resist pattern on a substrate by the method according to [9] or [10], and etching or plating the substrate.

  The photosensitive resin composition of the present invention is excellent in resolution and adhesiveness, can be developed with an alkaline aqueous solution, and further, the peeled piece can be dissolved in the peeling step. The resist pattern forming method of the present invention provides a resist pattern that is excellent in resolution and adhesion, and in which the resist strip can be dissolved in the step of stripping the resist pattern from the substrate. It can be suitably used for manufacturing, manufacturing of semiconductor packages, manufacturing of semiconductor bumps, and manufacturing of flat displays. Here, the peeling piece refers to a resist pattern piece peeled from the substrate.

Hereinafter, the present invention will be specifically described.
<Photosensitive resin composition>
The photosensitive resin composition of the present invention comprises (a) an α, β-unsaturated carboxyl group-containing monomer as a copolymerization component, an acid equivalent of 100 to 600, and a weight average molecular weight of 5,000 to 500,000. A thermoplastic copolymer of 20 to 90% by mass, (b) an addition polymerizable monomer having at least one terminal ethylenically unsaturated group: 5 to 75% by mass, and (c) a light containing a triarylimidazolyl dimer Polymerization initiator: 0.01 to 30% by mass is contained as an essential component, and the photocured portion of the photosensitive resin composition is soluble in the stripping solution.

Here, the photocured portion refers to a portion where the photosensitive resin composition is irradiated with light having a wavelength of 300 nm to 500 nm with an energy of 5 mJ / cm2 to 1000 J / cm2. The stripping solution is not particularly limited as long as the photocured resist pattern can be stripped from the substrate, and the pH is preferably 8 to 14 from the balance between the length of time required for stripping and the economy, and particularly 9 ~ 14 are preferred. An aqueous solution of NaOH and KOH having a concentration of 1 to 10% by mass and 40 to 70 ° C. is generally used. A small amount of a water-soluble solvent can also be added to the stripping solution.
The term “soluble” refers to a phenomenon in which the weight of the release piece decreases in the release solution.
Measure the weight of the strip before dipping in the stripper and the weight of the strip after dipping in the stripper, and the percentage of the strip after dipping in the stripper relative to the weight of the strip before dipping in the stripper The state of 5% or less is defined as “solubilization”. This value is preferably 4% or less, and more preferably 3% or less from the viewpoint of productivity.

(A) Thermoplastic copolymer In the photosensitive resin composition of the present invention, (a) as the thermoplastic copolymer, an acid equivalent containing an α, β-unsaturated carboxyl group-containing monomer as a copolymerization component. Having a weight average molecular weight of 5,000 to 500,000 is used.

  The carboxyl group in the thermoplastic copolymer is necessary for the photosensitive resin composition to have developability and releasability, in particular, releasability with respect to the developer and release solution made of an alkaline aqueous solution. Here, the releasability refers to the ease of peeling the resist pattern from the substrate.

  The acid equivalent is preferably 100 to 600, more preferably 250 to 450. It is 100 or more from the viewpoint of enabling dissolution in a stripping solution, and 600 or less from the viewpoint of maintaining developability. Here, an acid equivalent means the mass (gram) of the thermoplastic copolymer which has a 1 equivalent carboxyl group in it. The acid equivalent is measured using a Hiranuma Reporting Titrator (COM-555) by potentiometric titration with a 0.1 mol / l NaOH aqueous solution.

The weight average molecular weight is preferably 5,000 to 500,000. From the viewpoint of maintaining the thickness of the dry film resist uniformly and obtaining resistance to the developer, it is 5,000 or more, and from the viewpoint of maintaining the developability and enabling the solubility in the stripper. 000 or less. More preferably, the weight average molecular weight is 20,000 to 100,000. The weight average molecular weight in this case is a weight average molecular weight measured by gel permeation chromatography (GPC) using a standard curve of standard polystyrene (Shodex STANDARD SM-105 manufactured by Showa Denko KK). The weight average molecular weight can be measured using gel permeation chromatography manufactured by JASCO Corporation under the following conditions.
Differential refractometer: RI-1530,
Pump: PU-1580,
Degasser: DG-980-50,
Column oven: CO-1560,
Column: KF-8025, KF-806M × 2, KF-807, in order
Eluent: THF

  The thermoplastic copolymer is preferably a copolymer containing at least one or more first monomers described later, or at least one or more second monomers described later.

  The first monomer is a monomer containing an α, β-unsaturated carboxyl group in the molecule. Examples include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is particularly preferable from the viewpoint of enabling solubility in a stripping solution. Here, (meth) acryl indicates acryl and methacryl. The same applies hereinafter.

  The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl ( (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, vinyl alcohol esters such as vinyl acetate, (meth) Examples include acrylonitrile, styrene, and polymerizable styrene derivatives. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, and styrene are particularly preferable from the viewpoint of improving resolution and adhesion.

  The amount of the thermoplastic polymer contained in the photosensitive resin composition of the present invention is in the range of 20 to 90% by mass, and preferably in the range of 25 to 70% by mass. This amount is 20% by mass or more from the viewpoint of maintaining alkali developability and enabling solubility in a stripping solution, and the resist pattern formed by exposure exhibits sufficient performance as a resist. It is 90 mass% or less from a viewpoint of doing.

(B) Addition polymerizable monomer As the (b) addition polymerizable monomer used in the photosensitive resin composition of the present invention, a known compound having at least one terminal ethylenically unsaturated group can be used.

  For example, nonylphenoxypolyethoxypropoxyacrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxyhexaethylene glycol acrylate, a reaction product of a half ester compound of phthalic anhydride and 2-hydroxypropyl acrylate and propylene oxide (manufactured by Nippon Shokubai Chemical) , Trade name: OE-A200), pentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, 4-normal octylphenoxypentapropylene glycol acrylate, 1,6-hexanediol (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, or polyoxyalkylene glycol di (meth) acrylate, such as polypropylene Glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polyoxyethylene polyoxypropylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate And polyfunctional (meth) acrylates containing urethane groups, for example, urethanized products of hexamethylene diisocyanate and nonapropylene glycol monomethacrylate, and polyfunctional (meth) acrylates of isocyanuric acid ester compounds. These may be used alone or in combination of two or more.

  In particular, from the viewpoint of enabling solubility in a stripping solution, those containing 3 to 40 ethylene oxide chains are preferred, more preferably 4 to 32, and most preferably 6 to 30. Examples include polyethylene glycol di (meth) acrylate, polyoxyethylene polyoxypropylene glycol di (meth) acrylate, ethoxylated glycidyl tri (meth) acrylate, ethoxylated propoxylated glycidyl tri (meth) acrylate, ethoxylated Trimethylolpropane tri (meth) acrylate, ethoxylated propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated pentaerythritol penta (meth) acrylate, ethoxylated propoxylated pentaerythritol penta (meth) acrylate, ethoxy modified urethane di (meth) Acrylate (UA-11 Shin-Nakamura Kogyo), ε-caprolactone-modified tris ((meth) acryloxyethyl) isocyanurate, ethoxypropoxy modification Urethane di (meth) acrylate, nonylphenoxypolyethoxyacrylate (NP-8EA manufactured by Kyoeisha Chemical Co., Ltd.), nonylphenoxypolyethoxypropoxyacrylate and the like. The molecular weight of ethylene oxide with respect to the molecular weight of the whole addition polymerizable monomer is preferably 0.0002 to 0.95, more preferably 0.001 to 0.9, and most preferably 0.005 to 0.85.

  Further, for example, those having a functional group showing acidity such as a carboxyl group, a hydroxyl group, and a modified product thereof in the structure are also useful for improving the solubilization in the stripping solution. Examples of such include hydroxyalkyl (meth) acrylate, 2- (meth) acryloyloxyalkyl succinic acid, 2- (meth) acryloyloxyalkyl phthalic acid, 2- (meth) acryloyloxyalkyl hexahydrophthal Acid, 2- (meth) acryloyloxyalkyl hydroxyalkyl phthalate, glycerin di (meth) acrylate, chlorohydroxyalkyl (meth) acrylate, polyalkylene glycol diglycidyl ether, diglycidyl ether obtained by adding alkylene glycol to bisphenol A, water Diglycidyl ether obtained by adding alkylene glycol to bisphenol A, compound obtained by adding (meth) acrylic acid to diglycidyl ether obtained by adding alkylene glycol to bisphenol A, hydrogenated bisphenol A compound obtained by adding (meth) acrylic acid to diglycidyl ether obtained by adding alkylene glycol to A, pentaerythritol triacrylate, (meth) acrylic acid, glycidyl (meth) acrylate, (meth) acryloyloxyalkyl acid phosphate, Etc.

  Further, from the viewpoint of improving resolution and adhesion, the following general formula (I):

（式中、Ｒ_１及びＲ_２は、それぞれ独立にＨ又はＣＨ_３である。また、Ａ及びＢは炭素数２〜６のアルキレン基を示し、これらは同一であっても相違していてもよく、異なっている場合、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の繰り返し単位の配列は、ブロック構造でもランダム構造でもよい。ａ１、ａ２、ｂ１及びｂ２は、それぞれ独立に０又は正の整数であり、これらの合計は２〜４０の整数である。）で表される化合物、又は、下記一般式（ＩＩ）：

(In the formula, R ₁ and R ₂ are each independently H or CH ₃ , and A and B represent an alkylene group having 2 to 6 carbon atoms, which may be the same or different. When they are different, the arrangement of the repeating units of-(A-O)-and-(B-O)-may be a block structure or a random structure, and a1, a2, b1, and b2 are each independently 0. Or a positive integer, and the total of these is an integer of 2 to 40), or the following general formula (II):

（式中、Ｒ_３及びＲ_４は、それぞれ独立にＨ又はＣＨ_３である。また、Ｄ及びＥは炭素数２〜６のアルキレン基を示し、これらは同一であっても相違していてもよく、異なっている場合、−（Ｄ−Ｏ）−及び−（Ｅ−Ｏ）−の繰り返し単位の配列は、ブロック構造でもランダム構造でもよい。ａ３、ａ４、ｂ３及びｂ４は、それぞれ独立に０又は正の整数であり、これらの合計は２〜４０の整数である。）で示される化合物からなる群より選ばれる少なくとも一種の化合物が特に好ましい。

(In the formula, R ₃ and R ₄ are each independently H or CH ₃ , and D and E represent an alkylene group having 2 to 6 carbon atoms, which may be the same or different. When they are different, the arrangement of the repeating units of-(D-O)-and-(E-O)-may be a block structure or a random structure, and a3, a4, b3 and b4 are each independently 0. Or a positive integer, and the sum of these is an integer of 2 to 40.) At least one compound selected from the group consisting of compounds represented by:

  Specific examples of the compound represented by the above formula (I) include 2,2-bis {(4-acryloxypolyethyleneoxy) cyclohexyl} propane or 2,2-bis {(4-methacryloxypolyethyleneoxy) cyclohexyl}. Propane is mentioned. The polyethyleneoxy group possessed by the compound is monoethyleneoxy group, diethyleneoxy group, triethyleneoxy group, tetraethyleneoxy group, pentaethyleneoxy group, hexaethyleneoxy group, heptaethyleneoxy group, octaethyleneoxy group, nonaethylene It is any group selected from the group consisting of oxy group, decaethyleneoxy group, undecaethyleneoxy group, dodecaethyleneoxy group, tridecaethyleneoxy group, tetradecaethyleneoxy group, and pentadecaethyleneoxy group Compounds are preferred.

  Further, 2,2-bis {(4-acryloxypolyalkyleneoxy) cyclohexyl} propane or 2,2-bis {(4-methacryloxypolyalkyleneoxy) cyclohexyl} propane may also be mentioned. Examples of the polyalkyleneoxy group possessed by the compound include a mixture of an ethyleneoxy group and a propyleneoxy group, an adduct having a block structure or a random structure having an octaethyleneoxy group and a dipropyleneoxy group, and tetraethyleneoxy. An adduct having a block structure of a group and a tetrapropyleneoxy group or an adduct having a random structure, an adduct having a block structure of a pentadecaethyleneoxy group and a dipropyleneoxy group, or an adduct having a random structure is preferable. In the formula, the total of a1, a2, b1 and b2 is more preferably an integer of 2 to 30. Among these, 2,2-bis {(4-methacryloxypentaethyleneoxy) cyclohexyl} propane is most preferable.

  Specific examples of the compound represented by the formula (II) include 2,2-bis {(4-acryloxypolyethyleneoxy) phenyl} propane or 2,2-bis {(4-methacryloxypolyethyleneoxy) phenyl}. Propane is mentioned. The polyethyleneoxy group possessed by the compound is monoethyleneoxy group, diethyleneoxy group, triethyleneoxy group, tetraethyleneoxy group, pentaethyleneoxy group, hexaethyleneoxy group, heptaethyleneoxy group, octaethyleneoxy group, nonaethylene It is any group selected from the group consisting of oxy group, decaethyleneoxy group, undecaethyleneoxy group, dodecaethyleneoxy group, tridecaethyleneoxy group, tetradecaethyleneoxy group, and pentadecaethyleneoxy group Compounds are preferred.

  Further, 2,2-bis {(4-acryloxypolyalkyleneoxy) phenyl} propane or 2,2-bis {(4-methacryloxypolyalkyleneoxy) phenyl} propane can be given. Examples of the polyalkyleneoxy group possessed by the compound include a mixture of an ethyleneoxy group and a propyleneoxy group, an adduct having a block structure or a random structure having an octaethyleneoxy group and a dipropyleneoxy group, and tetraethyleneoxy. An adduct having a block structure of a group and a tetrapropyleneoxy group or an adduct having a random structure, an adduct having a block structure of a pentadecaethyleneoxy group and a dipropyleneoxy group, or an adduct having a random structure is preferable. In the formula, a3, a4, b3 and b4 are 0 or a positive integer, and the total of a3, a4, b3 and b4 is preferably an integer of 2 to 30. Among these, 2,2-bis {(4-methacryloxypentaethyleneoxy) phenyl} propane is most preferable. These may be used alone or in combination of two or more.

Content in the case of containing at least one compound selected from the group consisting of a compound represented by the above formula (I) and a compound represented by the above formula (II), contained in the photosensitive resin composition of the present invention Is preferably contained in the photosensitive resin composition in an amount of 5 to 40% by mass, more preferably 10 to 30% by mass. This amount is preferably 5% by mass or more from the viewpoint of developing high resolution and high adhesion, and is preferably 40% by mass or less from the viewpoint of suppressing cold flow and delayed peeling of the cured resist.
In the photosensitive resin composition of the present invention, from the viewpoint that the acrylate compound in the addition polymerizable monomer (b) is 70% by mass or more based on (b) enables solubility in a stripping solution. preferable.

  The amount of the (b) addition polymerizable monomer contained in the photosensitive resin composition of the present invention is in the range of 5 to 75% by mass, and more preferably in the range of 15 to 60% by mass. This amount is 5% by mass or more from the viewpoint of suppressing poor curing of the resist pattern and delaying the development time, and further improving the solubility in the stripping solution, and also reduces the cold flow and the peeling delay of the cured resist. From the viewpoint of suppression, it is 75% by mass or less.

(C) Photopolymerization initiator The photosensitive resin composition of the present invention contains (c) a photopolymerization initiator. It is preferable that a triarylimidazolyl dimer is included from the viewpoint of improving resolution and adhesion.

  Examples of the above-mentioned triarylimidazolyl dimer include, for example, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ′, 5′-diphenylimidazolyl dimer, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylimidazolyl dimer, 2,4,5-tris- (o-chlorophenyl) -diphenylimidazolyl dimer, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -imidazolyl dimer, 2, 2′-bis- (2-fluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3- Trifluoromethylphenyl) -4,4 ', 5,5'-tetrakis - (3-methoxyphenyl) - imidazolyl dimer,

2,2′-bis- (2,4-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2, 5-Difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,6-difluorophenyl) -4,4 ′ , 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,4-trifluorophenyl) -4,4 ', 5,5'-tetrakis -(3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3,5-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -Imidazolyl dimer, 2,2'-bis- (2,3 6-trifluoromethyl-phenyl) -4,4 ', 5,5'-tetrakis - (3-methoxyphenyl) - imidazolyl dimer,

2,2′-bis- (2,4,5-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,4,6-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,4, 5-tetrafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,4,6-tetrafluorophenyl) ) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, and 2,2′-bis- (2,3,4,5,6-pentafluorophenyl)- 4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl)- Imidazolyl dimer and the like. In particular, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer is a photopolymerization initiator having a high effect on resolution and adhesion, and is preferably used. These may be used alone or in combination of two or more.

  When the triarylimidazolyl dimer is contained in the photosensitive resin composition, the amount is preferably 0.01 to 30% by mass, more preferably 0.05 to 10% by mass, and most preferably 0. .1 to 5% by mass. This amount is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity, and is preferably 30% by mass or less from the viewpoint of maintaining high resolution. It is also possible to use a photopolymerization initiator other than the triarylimidazolyl dimer in combination.

As such a photopolymerization initiator, quinones such as 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone,
Aromatic ketones such as benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], 4,4′-bis (diethylamino) benzophenone, benzoin,
Benzoin ethers such as benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin, benzyl dimethyl ketal, benzyl diethyl ketal,
N-phenylglycines, such as N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine,

A combination of thioxanthones and alkylaminobenzoic acid, for example, a combination of ethylthioxanthone and ethyl dimethylaminobenzoate, a combination of 2-chlorothioxanthone and ethyl dimethylaminobenzoate, a combination of isopropylthioxanthone and ethyl dimethylaminobenzoate,
Oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzoin oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime,
Acridines such as 1,7-bis (9-acridinyl) heptane (manufactured by Asahi Denka Kogyo Co., Ltd., N-1717), 9-phenylacridine,
Thioxanthones such as diethyl thioxanthone, isopropyl thioxanthone, chlorothioxanthone,
Dialkylaminobenzoates such as ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate,
Pyrazolines such as 1-phenyl-3-styryl-5-phenyl-pyrazoline, 1- (4-tert-butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4- tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline.

  Among these, Michler's ketone or 4,4'-bis (diethylamino) benzophenone is particularly preferable from the viewpoint of resolution and adhesion.

(D) Polymerization inhibitor Furthermore, in order to improve the thermal stability and storage stability of the photosensitive resin composition of the present invention, it is preferable that the photosensitive resin composition contains a radical polymerization inhibitor and benzotriazoles. That is.

  Polymerization inhibitors include hydroxy aromatic compounds such as p-methoxyphenol and 2,6-di-tert-butyl-p-cresol, quinones such as phenbenzoquinone, p-toluquinone and p-xyloquinone, nitrosophenylhydroxyamine Aluminum salts, amines such as diphenylnitrosamine, phenyl-α-naphthylamine, heterocyclic compounds such as phenothiazine, pyridine, nitrobenzene, dinitrobenzene, chloranil, aryl force fighter, 2,2′-methylenebis (4-ethyl-6- tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), cuprous chloride, and the like. From the viewpoint of resolution and adhesion, the following general formula (III) :

｛式中、Ｘは、ハロゲン原子、水素原子、炭素数１〜２０のアルキル基、炭素数３〜１０のシクロアルキル基、アミノ基又は炭素数１〜２０のアルキル基で置換されてもよいフェニル基、ナフチル基を含むアリール基、アミノ基、メルカプト基、炭素数１〜１０のアルキルメルカプト基、アルキル基の炭素数が１〜１０のカルボキシアルキル基、炭素数１〜２０のアルコキシ基又は複素環であり、ｍ及びｎは、ｍが２以上の整数であり、ｎが０以上の整数であって、ｍ＋ｎ＝６となるように選ばれる整数であり、ｎが２以上の整数の時、２以上のＸは各々同一でも相違してもよい｝で示される化合物が好ましい。

{In the formula, X is phenyl optionally substituted by a halogen atom, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an amino group, or an alkyl group having 1 to 20 carbon atoms. Group, aryl group including naphthyl group, amino group, mercapto group, alkyl mercapto group having 1 to 10 carbon atoms, carboxyalkyl group having 1 to 10 carbon atoms in alkyl group, alkoxy group having 1 to 20 carbon atoms or heterocyclic ring M and n are integers selected so that m is an integer of 2 or more, n is an integer of 0 or more, and m + n = 6, and when n is an integer of 2 or more, 2 The compounds represented by the above X may be the same or different are preferred.

  X in the compound represented by the general formula (III) is a halogen atom, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an amino group, or an alkyl group having 1 to 20 carbon atoms. Aryl group such as phenyl group and naphthyl group which may be substituted with alkyl group, amino group, mercapto group, alkylmercapto group having 1 to 10 carbon atoms, carboxyalkyl group having 1 to 10 carbon atoms in alkyl group, carbon The group which consists of a C1-C20 alkoxy group or a heterocyclic ring is shown, and it is especially preferable that it is an alkyl group.

  Examples of the halogen atom include fluorine, chlorine, bromine, iodine, and astatine. Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, and octyl group. , Nonyl group, decyl group, undecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, nonadecyl group, icosyl group and the like.

Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the aryl group substituted with an alkyl group having 1 to 20 carbon atoms include a methylphenyl group, an ethylphenyl group, and a propylphenyl group.
As said C1-C10 alkyl mercapto group, a methyl mercapto group, an ethyl mercapto group, a propyl mercapto group etc. are mentioned, for example. Examples of the carboxyalkyl group having 1 to 10 carbon atoms of the alkyl group include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, and a carboxybutyl group.
As said C1-C20 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned, for example. Examples of the group consisting of the heterocyclic ring include an ethylene oxide group, a furan group, a thiophene group, a pyrrole group, a thiazole group, an indole group, and a quinoline group. In the general formula (I), m and n are integers selected such that m is an integer of 2 or more, n is an integer of 0 or more, and m + n = 6. When n is an integer of 2 or more, 2 or more Xs may be the same or different. From the viewpoint of resolution, m is preferably an integer of 2 or more.

  Moreover, as a compound represented by the said general formula (I) of (D) component of this invention, catechol, resorcinol (resorcin), 1, 4- hydroquinone, 2-methylcatechol, 3-methylcatechol, 4 -Methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4- Alkyl catechol such as n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol, 3,5-di-tert-butyl catechol, 2-methylresorcinol, 4-methylresorcinol , 5-methylresorcinol (Orsi ), 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, etc. Alkylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, alkylhydroquinone such as 2,5-di-tert-butylhydroquinone, pyrogallol, and phloroglucin.

  Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzo. Examples include triazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole. Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl). Examples include aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole.

The total addition amount of the radical polymerization inhibitor and the benzotriazoles is preferably 0.01 to 3% by mass, and more preferably 0.05 to 1% by mass. This amount is preferably 0.01% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and is preferably 3% by mass or less from the viewpoint of maintaining photosensitivity.
These radical polymerization inhibitors and benzotriazole compounds may be used alone or in combination of two or more.

(E) Other components In the photosensitive resin composition of the present invention, in addition to the components described above, coloring substances represented by dyes and pigments can be employed. Examples of such coloring substances include phthalocyanine green, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, basic blue 20 and diamond green.

  Moreover, you may add a leuco dye in the photosensitive resin composition of this invention so that a visible image can be given by exposure. Such leuco dyes include leuco crystal violet and fluoran dyes. Among these, when leuco crystal violet is used, the contrast is good and preferable. Examples of the fluorane dye include 3-diethylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, and 2- (2-chloroanilino) -6-dibutylamino. Fluorane, 2-bromo-3-methyl-6-dibutylaminofluorane, 2-N, N-dibenzylamino-6-diethylaminofluorane, 3-diethylamino-7-chloroaminofluorane, 3,6-dimethoxy Fluorane, 3-diethylamino-6-methoxy-7-aminofluorane and the like can be mentioned.

  Use of a combination of a leuco dye and a halogen compound in the photosensitive resin composition is a preferred embodiment from the viewpoint of adhesion and contrast.

  Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, halogenated triazine compounds and the like. .

  When the halogen compound is contained, the content of the halogen compound in the photosensitive resin composition is preferably in the range of 0.01 to 5% by mass.

  The content of the coloring substance and the leuco dye is preferably in the range of 0.01 to 10% by mass in the photosensitive resin composition. The amount is preferably 0.01% by mass or more from the viewpoint that sufficient colorability (coloring property) can be recognized, and is preferably 10% by mass or less from the viewpoint of maintaining the contrast between the exposed part and the unexposed part and maintaining storage stability.

  You may make the photosensitive resin composition of this invention contain a plasticizer as needed. Examples of such a plasticizer include glycol esters; for example, polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl. Ethers, polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, phthalates; for example, diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, Tributyl citrate, triethyl citrate, acetyl triethyl citrate, tri-n-propyl acetyl citrate, acetyl citrate Tri -n- butyl.

  It is preferable that 5-50 mass% of plasticizers are contained in the photosensitive resin composition, More preferably, it is the range of 5-30 mass%. 5 mass% or more is preferable from the viewpoint of suppressing development time delay, imparting flexibility to a cured film, and improving solubility in a stripping solution, and 50 mass from the viewpoint of suppressing insufficient curing and cold flow. % Or less is preferable.

  The photosensitive resin composition of the present invention may contain a solvent in order to obtain a preparation solution in which the above (a) to (e) are uniformly dissolved. Examples of the solvent used include ketones typified by methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropyl alcohol. From the viewpoint of coating properties when formed into a film, it is preferable to prepare a solvent so that the viscosity of the preparation liquid of the photosensitive resin composition is 500 to 4000 mPa · sec at 25 ° C.

<Photosensitive resin laminate>
The photosensitive resin laminate of the present invention comprises a photosensitive resin layer and a support that supports the layer. If necessary, the photosensitive resin laminate may have a protective layer on the surface opposite to the support of the photosensitive resin layer. good.

  The support used here is preferably a transparent one that transmits light emitted from the exposure light source. Examples of such a support include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, Examples include polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films can be stretched if necessary. The haze is preferably 5 or less. The thinner the film, the more advantageous in terms of image forming property, stripping solution solubility, and economic efficiency. However, a film having a thickness in the range of 10 to 30 μm is preferably used because the strength needs to be maintained.

  Further, an important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support and can be easily peeled with respect to the adhesion with the photosensitive resin layer. For example, a polyethylene film or a polypropylene film can be preferably used as the protective layer. Also, a film having excellent peelability disclosed in JP-A-59-202457 can be used.

10-100 micrometers is preferable and, as for the film thickness of a protective layer, 10-50 micrometers is more preferable.
The thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the use, but is preferably in the range of 5 to 100 μm, more preferably 7 to 60 μm. The thinner the resolution, the better the film strength. improves.

  A conventionally well-known method can be employ | adopted for the method of laminating | stacking a support body, the photosensitive resin layer, and the protective layer if needed, and producing the photosensitive resin laminated body of this invention.

  For example, the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent that dissolves them to form a uniform solution, and is first coated on a support using a bar coater or roll coater, dried, and then supported. A photosensitive resin layer made of a photosensitive resin composition is laminated on the body.

  Next, if necessary, a photosensitive resin laminate can be prepared by laminating a protective layer on the photosensitive resin layer.

<Resist pattern formation method>
A resist pattern using the photosensitive resin laminate of the present invention can be formed by a process including a lamination process, an exposure process, and a development process.

  As an example of a specific method, first, a laminating process is performed using a laminator. In the case where the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed and laminated on the substrate surface with a laminator. In this case, the photosensitive resin layer may be laminated only on one side of the substrate surface or on both sides. The heating temperature at this time is generally 40 to 160 ° C. Moreover, adhesion and chemical resistance are improved by performing the thermocompression bonding twice or more. At this time, for the crimping, a two-stage laminator having two rolls may be used, or it may be repeatedly crimped through the roll several times.

  Next, the exposure process which exposes active light using an exposure machine is performed. If necessary, the support is peeled off and exposed to active light through a photomask. The exposure amount is determined from the light source illuminance and the exposure time. You may measure using a photometer.

  In the exposure process, a maskless exposure method may be used. In maskless exposure, exposure is performed by directly drawing on a substrate without using a photomask. As the light source, a semiconductor laser having a wavelength of 350 to 410 nm, an ultrahigh pressure mercury lamp, or the like is used. The drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the light source illuminance and the moving speed of the substrate.

Next, a developing process is performed in which the unexposed portions of the photosensitive resin layer are dispersed and removed using a developing device. After the exposure, if there is a support on the photosensitive resin layer, this is removed if necessary, and then the unexposed portion is developed and removed using a developer that is an alkaline aqueous solution to obtain a resist image. An aqueous solution of Na ₂ CO ₃ , K ₂ CO ₃ or the like is used as the alkaline aqueous solution. These are selected in accordance with the characteristics of the photosensitive resin layer, but a Na ₂ CO ₃ aqueous solution having a concentration of 0.2 to 2% by mass and 20 to 40 ° C. is generally used. A surface active agent, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution.

  Although a resist pattern is obtained by the above-mentioned process, a heating process at 100 to 300 ° C. can be further performed depending on the case. By carrying out this heating step, chemical resistance can be further improved. For heating, a heating furnace having a system such as hot air, infrared rays, and far infrared rays can be used.

<Method for manufacturing printed wiring board>
The manufacturing method of the printed wiring board of this invention is performed by forming a resist pattern by the above-mentioned resist pattern formation method using a copper clad laminated board and a flexible substrate as a board | substrate, and passing through the following processes subsequently.
First, a conductive pattern is formed on the copper surface of the substrate exposed by development using a known method such as an etching method or a plating method.
Thereafter, the resist pattern is dissolved or peeled from the substrate with an aqueous solution having alkalinity stronger than that of the developer to obtain a desired printed wiring board. The stripping solution is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of 1 to 10% by mass and 40 to 70 ° C. is generally used. A small amount of a water-soluble solvent can also be added to the stripping solution.

<Lead frame manufacturing method>
The manufacturing method of the lead frame of the present invention forms a resist pattern by the above-described resist pattern forming method using a metal plate such as copper, copper alloy, iron-based alloy as a substrate, and then undergoes the following steps. Is done.
First, a conductive pattern is formed by etching the substrate exposed by development.
Thereafter, the resist pattern is peeled off from the conductor pattern by a method similar to the above-described printed wiring board manufacturing method to obtain a desired lead frame.

<Semiconductor package manufacturing method>
The semiconductor package manufacturing method of the present invention is performed by forming a resist pattern by the above-described resist pattern forming method using a wafer on which circuit formation as an LSI has been completed as a substrate, and subsequently performing the following steps. .
A conductor pattern is formed by performing columnar plating such as copper or solder on the opening exposed by development.
Thereafter, the resist pattern is peeled by the same method as the above-described printed wiring board manufacturing method, and the thin metal layer other than the columnar plating is removed by etching to obtain a desired semiconductor package.

<Semiconductor bump manufacturing method>
The semiconductor bump manufacturing method of the present invention is performed by forming a resist pattern by the above-described resist pattern forming method using a wafer on which an LSI circuit has been formed as a substrate, and subsequently performing the following steps. .
A conductor pattern is formed by performing columnar plating such as copper or solder on the opening exposed by development. After this step, reflow may be performed at a high temperature of 100 to 300 ° C.
Thereafter, the resist pattern is stripped by the same method as the above-described printed wiring board manufacturing method, and the thin metal layer other than the columnar plating is removed by etching to obtain a desired semiconductor bump.

<Method for manufacturing uneven substrate>
When the photosensitive resin laminate of the present invention is used as a dry film resist and the substrate is processed by the sand blasting method, the lamination is performed by laminating the photosensitive resin laminate on the substrate in the same manner as described above. Process, exposure and development. Further, a blasting material is sprayed from the formed resist pattern to be cut to a desired depth, and a resin part remaining on the base material is removed from the base material with an alkaline stripping solution, etc. A substrate having an uneven pattern, that is, an uneven substrate can be obtained. As the blasting material used in the above sandblasting process, known materials are used, for example, fine particles of about ₂ to 100 μm such as SiC, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO ₂ , glass, stainless steel, etc. are used. . The uneven substrate can be suitably used, for example, as a back plate for a flat display.

<Method for measuring solubility of peeled piece>
The resist pattern obtained on the substrate after etching or plating was immersed in a 3% aqueous sodium hydroxide solution at 70 ° C. for 30 minutes, and the solubility of the peeled pieces was observed with the naked eye. Further, the substrate was taken out and dried, and the total weight before and after immersion was measured.
(Weight after immersion) / (Weight before immersion) x 100 (%)
In this case, the case where it was 5% or less was defined as “dissolved in the stripping solution”.

EXAMPLES The present invention will be described more specifically with reference to examples below, but the present invention is not limited to these examples.
First, a method for producing samples for evaluation of Examples and Comparative Examples will be described, and then an evaluation method and evaluation results for the obtained samples will be shown.

[Examples 1-6, Comparative Examples 1-3]

1. Production of Evaluation Samples The photosensitive resin laminates in Examples 1 to 6 and Comparative Examples 1 to 3 were produced as follows.
<Preparation of photosensitive resin laminate>
The photosensitive resin composition and solvent having the composition shown in Table 1 are thoroughly stirred and mixed, and uniformly coated on the surface of a polyethylene terephthalate film having a thickness of 16 μm as a support using a bar coater. The photosensitive resin layer was formed by drying for a minute. The thickness of the photosensitive resin layer was 15 μm.
Next, a 23 μm thick polyethylene film was laminated as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate.
Table 2 shows the names of the material components in the photosensitive resin composition represented by abbreviations in Table 1.
In addition, Comparative Examples 1-2 is a composition which does not contain the component which can be melt | dissolved in a peeling piece. Moreover, the comparative example 3 is a composition which does not contain the (c) triaryl imidazolyl dimer used for this invention.

<Board surface preparation>
The substrate for sensitivity and resolution evaluation was prepared by jet scrub polishing (Nippon Carlit Co., Ltd., Sac Random R (registered trademark) # 220) at a spray pressure of 0.20 MPa.
<Laminate>
While peeling off the polyethylene film of the photosensitive resin laminate, it was laminated at a roll temperature of 105 ° C. with a hot roll laminator (Asahi Kasei Engineering Co., Ltd., AL-70) on a copper clad laminate that had been leveled and preheated to 60 ° C. . The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.
<Exposure>
The photosensitive resin layer was exposed to 100 mJ / cm ² with a super high pressure mercury lamp (OMW Seisakusho HMW-801) through the support without a photomask or through a photomask necessary for evaluation.

<Development>
After the polyethylene terephthalate film was peeled off, a 1 mass% Na2CO3 aqueous solution at 30 [deg.] C. was sprayed for a predetermined time to dissolve and remove the unexposed portion of the photosensitive resin layer. At this time, the minimum time required for completely dissolving the photosensitive resin layer in the unexposed portion was defined as the minimum development time.
<Etching>
The developed substrate was etched with a salt copper etching apparatus (manufactured by Tokyo Chemical Industry Co., Ltd.) at 3 mol / l hydrochloric acid, 250 g / l cupric chloride at 50 ° C. for 1.3 times the minimum etching time. At this time, the time when the copper foil on the substrate was completely dissolved and removed was defined as the minimum etching time.
<Resist stripping>
The developed evaluation substrate was immersed in a 3% by mass aqueous sodium hydroxide solution heated to 70 ° C. and stirred with a stirrer for 30 minutes. The stirring speed was 300 rpm.

2. Evaluation Method (1) Resolution Evaluation A substrate for sensitivity and resolution evaluation 15 minutes after lamination was exposed through a line pattern mask in which the width of the exposed area and the unexposed area was 1: 1. Development was performed with a development time twice as long as the minimum development time, and the minimum mask line width at which a cured resist line was normally formed was defined as a resolution value.
○: The resolution value is 10 μm or less.
(Triangle | delta): The value of resolution exceeds 10 micrometers and is 15 micrometers or less.
X: The value of resolution exceeds 15 μm.

(2) Adhesion Evaluation The substrate for sensitivity and resolution evaluation 15 minutes after lamination was exposed through a line pattern mask in which the width of the exposed area and the unexposed area was 1: 1. Development was carried out with a development time twice as long as the minimum development time, and the minimum mask width that was normally formed on the cured resist line was defined as the adhesion value.
○: Adhesion value is 10 μm or less.
(Triangle | delta): The value of adhesiveness exceeds 10 micrometers and is 15 micrometers or less.
X: Adhesion value exceeds 15 μm.

(3) Solubility Evaluation in Stripping Solution After the substrate was etched, the resulting pattern was cut into 10 cm × 10 cm. Thereafter, it was immersed in a 3% aqueous sodium hydroxide solution at 70 ° C. for 30 minutes, and the solubility of the peeled pieces was observed with the naked eye. Further, the substrate was taken out and dried, and the total weight before and after immersion was measured.
(Peeling weight after immersion) / (Peeling weight before immersion) x 100 (%)
Based on the formula, the ranking was performed as follows.

○: Weight is 5% or less ×: Weight is greater than 5% (4) Yield evaluation In the process of peeling the resist pattern from the substrate, the ratio (defect rate) of the peeled pieces adhering to the substrate is measured. The ranking was performed as follows.
○: Failure rate is 5% or less ×: Failure rate is 5% or more

3. Evaluation results The evaluation results of Examples and Comparative Examples are shown in Tables 1 and 2 below.

The present invention relates to the manufacture of printed wiring boards, the manufacture of flexible printed wiring boards, the manufacture of lead frames for mounting IC chips, the manufacture of metal foils such as the manufacture of metal masks, the manufacture of packages such as BGA and CSP, and the tapes such as COF and TAB. It can be used for the production of substrates, the production of semiconductor bumps, the production of partition walls for flat panel displays such as ITO electrodes, address electrodes, and electromagnetic wave shields, and the method of processing a substrate by sandblasting.
Examples of the processing by the sandblasting method include organic EL glass cap processing, drilling processing of a silicon wafer, and ceramic pinning processing.
Furthermore, the processing by the sand blasting process of the present invention can be used for manufacturing an electrode of a metal material layer selected from the group consisting of a ferroelectric film and a noble metal, a noble metal alloy, a refractory metal, and a refractory metal compound.

Claims (15)

  (A) Thermoplastic copolymer containing an α, β-unsaturated carboxyl group-containing monomer as a copolymerization component and having an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000: 20 to 90 (B) Addition polymerizable monomer having at least one terminal ethylenically unsaturated group: 5 to 75% by mass, and (c) Photopolymerization initiator containing triarylimidazolyl dimer: 0.01 to 30 A photosensitive resin composition containing% by mass, wherein a photocured part of the photosensitive resin composition is soluble in a stripping solution.   (B) The photosensitive resin composition of Claim 1 in which the addition polymerizable monomer which has an at least 1 terminal ethylenically unsaturated group contains 3-40 ethylene oxide chains. (B) An addition polymerizable monomer having at least one terminal ethylenically unsaturated group is represented by the following general formula (I):

{Wherein R ₁ and R ₂ are each independently H or CH ₃ , and A and B are each independently an alkylene group having 2 to 4 carbon atoms, a1, a2, b1 and b2 are each a positive integer, and the sum of a1, a2, b1, and b2 is an integer of 2 to 40, and-(A-O)-and-(B-O)- The arrangement of repeating units may be a block or random. } Or the following general formula (II):

{Wherein R ₃ and R ₄ are each independently H or CH ₃ , D and E are each independently an alkylene group having 2 to 4 carbon atoms, and a 3, a 4, b 3 and b4 is a positive integer, respectively, and the sum of a3, a4, b3 and b4 is 2 to 40, and-(DO)-and-(EO)- The arrangement can be random, even in blocks. The photosensitive resin composition according to claim 1 or 2, which is at least one compound selected from the group consisting of compounds represented by: (D) General formula (III):

{In the formula, X is phenyl optionally substituted by a halogen atom, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an amino group, or an alkyl group having 1 to 20 carbon atoms. Group, aryl group including naphthyl group, amino group, mercapto group, alkyl mercapto group having 1 to 10 carbon atoms, carboxyalkyl group having 1 to 10 carbon atoms in alkyl group, alkoxy group having 1 to 20 carbon atoms or heterocyclic ring M and n are integers selected so that m is an integer of 2 or more, n is an integer of 0 or more, and m + n = 6, and when n is an integer of 2 or more, 2 The above Xs may be the same or different. } The photosensitive resin composition of any one of Claims 1-3 which further contains the compound represented by these.   (A) The photosensitive resin composition of Claim 1 in which a thermoplastic copolymer contains the monomer which has at least one polymerizable unsaturated group as a copolymerization component.   The photosensitive resin composition of any one of Claims 3-5 in which the compound represented by the said general formula (I) or general formula (II) has a polyethyleneoxy group.   (B) The photosensitive resin composition of Claim 1 whose 70 mass% or more is acrylates in the said addition polymerizable monomer which has an at least 1 terminal ethylenically unsaturated group.   The photosensitive resin laminated body formed by laminating | stacking the photosensitive resin composition of any one of Claims 1-7 on a support body.   A resist pattern forming method comprising a lamination step of forming a photosensitive resin layer on the substrate using the photosensitive resin laminate according to claim 8, an exposure step, and a development step of removing unexposed portions.   The resist pattern forming method according to claim 9, wherein in the exposure step, exposure is performed by direct drawing.   The manufacturing method of a printed wiring board including the process of forming a resist pattern on a board | substrate by the method of Claim 9 or 10, and etching or plating this board | substrate.   A method for manufacturing a lead frame, comprising: forming a resist pattern on a substrate by the method according to claim 9 or 10; and etching the substrate.   A method for producing a concavo-convex substrate, comprising a step of forming a resist pattern on a substrate by the method according to claim 9 or 10 and sandblasting the substrate.   A method of manufacturing a semiconductor package, comprising: forming a resist pattern on a substrate by the method according to claim 9 or 10; and etching or plating the substrate.   A method for producing a semiconductor bump, comprising: forming a resist pattern on a substrate by the method according to claim 9 or 10; and etching or plating the substrate.