JP2011075706A - Photosensitive resin composition, photosensitive resin laminate, resist pattern-forming method, and method for producing conductor pattern, printed wiring board, lead frame, substrate with uneven pattern and semiconductor package - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which is excellent in sensitivity, resolution and interface adhesion of a resist hem and ensures small size of stripped pieces in stripping and good treatability of waste liquid. <P>SOLUTION: The photosensitive resin composition comprises: (a) a thermoplastic polymer polymerized from a polymerizing component including an α,β-unsaturated carboxyl group-containing monomer, the polymer having a specific acid equivalent and a specific weight average molecular weight; (b) an addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in a molecule; and (c) a photoinitiator, each in a specific amount, wherein (a-1) a polymer having a weight average molecular weight of 15,000-85,000 and (a-2) a polymer having a weight average molecular weight of 150,000-400,000 are included as the thermoplastic polymer (a) in a polymer (a-1) to (a-2) mass ratio of 1-3, and wherein a proportion of a polymerizing component containing an aromatic group to the above polymerizing component is ≤10 mass%. <P>COPYRIGHT: (C)2011,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. The present invention relates to a method for forming the resist pattern and an application 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 IC chip mounting (hereinafter simply referred to as lead frames), metal foil precision processing such as metal mask manufacturing, BGA (ball grid array) Manufacturing of semiconductor substrates such as CSP (chip size package), tape substrates represented by TAB (Tape Automated Bonding) and COF (Chip On Film: a semiconductor IC mounted on a film-like fine wiring board), The present invention relates to a photosensitive resin composition that provides a resist pattern suitable for the manufacture of semiconductor bumps and the manufacture of members such as ITO electrodes, address electrodes, and electromagnetic wave shields in the field of flat panel displays.

  Conventionally, printed wiring boards are manufactured by a photolithography method. According to the photolithography method, a photosensitive resin composition is applied onto a substrate, pattern exposure is performed to polymerize and cure an exposed portion of the photosensitive resin composition, and an unexposed portion is removed with a developing solution to form on the substrate. After a resist pattern is formed and a conductor pattern is formed by etching or plating, the conductor pattern can be formed on the substrate by removing the resist pattern from the substrate.

  In the above-described photolithography method, when the photosensitive resin composition is applied onto the substrate, usually, a method of applying the photosensitive resin composition to the substrate and drying it, or a support, from the photosensitive resin composition A method of laminating a photosensitive resin laminate (hereinafter also referred to as “dry film resist”) in which a layer (hereinafter also referred to as “photosensitive resin layer”) and a protective layer as necessary are sequentially laminated on a substrate. One of these 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 the dry film resist has a protective layer such as a polyethylene film, it is peeled off from the photosensitive resin layer. Next, using a laminator, the photosensitive resin layer and the support are laminated on a substrate such as a copper clad laminate 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 such as i-line (365 nm) 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. In the method of removing the metal portion by etching, the metal in the hole is prevented from being etched by covering the through hole (through hole) of the substrate and the via hole for interlayer connection with a cured resist film. This construction method is called a tenting method. Finally, the resist pattern is peeled from the substrate with an aqueous alkali solution such as sodium hydroxide to produce a substrate having a conductor pattern, that is, a printed wiring board. In the method of plating, after performing plating treatment of copper, solder, nickel, tin, etc. on the copper surface on which the resist pattern is formed, the resist pattern portion is similarly peeled and removed, and the copper-clad laminate that appeared The copper surface is etched and finally the plating is peeled off. In the etching process described above, cupric chloride, ferric chloride, a copper ammonia complex solution, or the like is used.

  In the resist pattern peeling process, when the size of the peeled piece of the cured resist film is large, the entanglement of the peeling layer with the ring roll may be a problem. Further, when plating is performed, the plating often overhangs. In this case, if the peeling piece is not fine, peeling failure may occur and the resist film may remain on the substrate. Therefore, there is a need for a technique for making the peeled pieces fine. Patent Documents 1 to 3 propose a technique for reducing the size of a peeled piece by using a low molecular weight thermoplastic polymer.

JP-A-1-55550 JP-A 63-266448 JP-A-11-327138

  However, the adhesion between the resist pattern and copper after development is poor, and if the sedge floats, the penetration of the etching solution and the plating solution will occur in the subsequent process, causing the shorting and backlash of the conductor pattern. Therefore, it is desired to develop a dry film resist which does not float due to good resist soso interface adhesion.

  In recent years, attention has been paid to the disposability of waste liquid generated in the printed wiring board manufacturing process due to environmental considerations, and a dry liquid that can quickly process waste liquid in an acid scum sedimentation process (hereinafter also referred to as acid precipitation). A film is desired.

  The present invention has excellent resistosso interface adhesion while maintaining good sensitivity and resolution, has a fine strip size when stripped with an alkaline aqueous solution of a photocured film, and has a waste liquid acid precipitation property (i.e., waste liquid treatability). Photosensitive resin composition that is good, photosensitive resin laminate using the photosensitive resin composition, method for forming a resist pattern on a substrate using the photosensitive resin laminate, and use of the resist pattern The purpose is to provide.

  The above object can be achieved by the following configuration of the present invention.

（式中、Ｒ₁及びＲ₂は各々独立にＨ又はＣＨ₃であり、そしてｎ₁、ｎ₂及びｎ₃は各々独立に３〜２０の整数である。）
で表される光重合可能な不飽和化合物及び下記一般式（ＩＩ）：

（式中、Ｒ₃及びＲ₄は各々独立にＨ又はＣＨ₃であり、ＡはＣ₂Ｈ₄であり、ＢはＣ₃Ｈ₆であり、ｎ₄及びｎ₅は各々独立に１〜２９の整数でかつｎ₄＋ｎ₅は２〜３０の整数であり、ｎ₆及びｎ₇は各々独立に０〜２９の整数でかつｎ₆＋ｎ₇は０〜３０の整数であり、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよく、ブロックの場合、−（Ａ−Ｏ）−と−（Ｂ−Ｏ）−とのいずれがビスフェニル基側でもよい。）
で表される光重合可能な不飽和化合物からなる群から選択される１種以上を含有する、上記［１］又は［２］に記載の感光性樹脂組成物。
［４］ 上記［１］〜［３］のいずれかに記載の感光性樹脂組成物が支持体上に積層されてなる感光性樹脂積層体。
［５］ 上記［４］に記載の感光性樹脂積層体を基板上に形成するラミネート工程、
該感光性樹脂積層体に露光する露光工程、及び
該感光性樹脂積層体における感光性樹脂の未露光部分を除去してレジストパターンを形成する現像工程
を含む、レジストパターン形成方法。
［６］ 上記［４］に記載の感光性樹脂積層体を、金属板又は金属皮膜絶縁板である基板上に形成するラミネート工程、
該感光性樹脂積層体に露光する露光工程、
該感光性樹脂積層体における感光性樹脂の未露光部分を除去してレジストパターンを形成する現像工程、及び
該レジストパターンが形成された基板をエッチング又はめっきすることによって導体パターンを形成する工程
を含む、導体パターンの製造方法。
［７］ 上記［４］に記載の感光性樹脂積層体を、銅張積層板又はフレキシブル基板である基板上に形成するラミネート工程、
該感光性樹脂積層体に露光する露光工程、
該感光性樹脂積層体における感光性樹脂の未露光部分を除去してレジストパターンを形成する現像工程、
該レジストパターンが形成された基板をエッチング又はめっきする工程、及び
該基板から該レジストパターンを剥離する工程を含む、プリント配線板の製造方法。
［８］ 上記［４］に記載の感光性樹脂積層体を、金属板である基板上に形成するラミネート工程、
該感光性樹脂積層体に露光する露光工程、
該感光性樹脂積層体における感光性樹脂の未露光部分を除去してレジストパターンを形成する現像工程、
該レジストパターンが形成された基板をエッチングする工程、及び
該基板から該レジストパターンを剥離する工程
を含む、リードフレームの製造方法。
［９］ 上記［４］に記載の感光性樹脂積層体を基板上に形成するラミネート工程、
該感光性樹脂積層体に露光する露光工程、
該感光性樹脂積層体における感光性樹脂の未露光部分を除去してレジストパターンを形成する現像工程、
該レジストパターンが形成された基板をサンドブラスト処理加工する工程、及び
該基板から該レジストパターンを剥離する工程
を含む、凹凸パターンを有する基板の製造方法。
［１０］ 上記［４］に記載の感光性樹脂積層体を、ＬＳＩとしての回路形成が完了したウェハである基板上に形成するラミネート工程、
該感光性樹脂積層体に露光する露光工程、
該感光性樹脂積層体における感光性樹脂の未露光部分を除去してレジストパターンを形成する現像工程、
該レジストパターンが形成された基板をめっきする工程、及び
該基板から該レジストパターンを剥離する工程
を含む、半導体パッケージの製造方法。 [1] (a) Thermoplastic polymerized from a polymerization component containing an α, β-unsaturated carboxyl group-containing monomer and having an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000 20 to 90% by mass of polymer, (b) 3 to 75% by mass of addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule, and (c) 0.01 to 30 photopolymerization initiator. A photosensitive resin composition containing mass%,
(A) As a thermoplastic polymer, (a-1) a polymer having a weight average molecular weight of 15,000 or more and 85,000 or less, and (a-2) a weight having a weight average molecular weight of 150,000 or more and 400,000 or less. A mass ratio (a-1) / (a-2) of the (a-1) polymer to the (a-2) polymer is 1 to 3, and The photosensitive resin composition whose ratio of the copolymer containing an aromatic group as a polymerization component is 10 mass% or less.
[2] The photosensitive resin composition according to the above [1], which contains a hexaarylbisimidazole derivative as the (c) photopolymerization initiator.
[3] As an addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule (b), the following general formula (I):

(Wherein R ₁ and R ₂ are each independently H or CH ₃ , and n ₁ , n ₂ and n ₃ are each independently an integer of 3 to 20).
And a photopolymerizable unsaturated compound represented by the following general formula (II):

Wherein R ₃ and R ₄ are each independently H or CH ₃ , A is C ₂ H ₄ , B is C ₃ H ₆ , and n ₄ and n ₅ are each independently 1 to 29 N ₄ + n ₅ is an integer of 2-30, n ₆ and n ₇ are each independently an integer of 0-29, and n ₆ + n ₇ is an integer of 0-30, and-(A- The arrangement of repeating units of O)-and-(B-O)-may be random or block. In the case of a block,-(A-O)-and-(B-O)- Any of these may be on the bisphenyl group side.)
The photosensitive resin composition as described in [1] or [2] above, which contains one or more selected from the group consisting of photopolymerizable unsaturated compounds represented by the formula:
[4] A photosensitive resin laminate obtained by laminating the photosensitive resin composition according to any one of [1] to [3] on a support.
[5] A laminating step for forming the photosensitive resin laminate according to the above [4] on a substrate,
A resist pattern forming method comprising: an exposure step of exposing the photosensitive resin laminate; and a developing step of forming a resist pattern by removing an unexposed portion of the photosensitive resin in the photosensitive resin laminate.
[6] A laminating step of forming the photosensitive resin laminate according to the above [4] on a substrate that is a metal plate or a metal film insulating plate,
An exposure step of exposing the photosensitive resin laminate;
A development step of removing a non-exposed portion of the photosensitive resin in the photosensitive resin laminate to form a resist pattern, and a step of forming a conductor pattern by etching or plating the substrate on which the resist pattern is formed. The manufacturing method of a conductor pattern.
[7] A laminating step of forming the photosensitive resin laminate according to the above [4] on a substrate that is a copper-clad laminate or a flexible substrate,
An exposure step of exposing the photosensitive resin laminate;
A development step of removing a non-exposed portion of the photosensitive resin in the photosensitive resin laminate to form a resist pattern;
A method for manufacturing a printed wiring board, comprising: a step of etching or plating a substrate on which the resist pattern is formed; and a step of peeling the resist pattern from the substrate.
[8] A laminating step of forming the photosensitive resin laminate according to the above [4] on a substrate that is a metal plate,
An exposure step of exposing the photosensitive resin laminate;
A development step of removing a non-exposed portion of the photosensitive resin in the photosensitive resin laminate to form a resist pattern;
A method of manufacturing a lead frame, comprising: etching a substrate on which the resist pattern is formed; and peeling the resist pattern from the substrate.
[9] A laminating step for forming the photosensitive resin laminate according to the above [4] on a substrate,
An exposure step of exposing the photosensitive resin laminate;
A development step of removing a non-exposed portion of the photosensitive resin in the photosensitive resin laminate to form a resist pattern;
A method for manufacturing a substrate having a concavo-convex pattern, comprising: a step of subjecting a substrate on which the resist pattern is formed to a sandblasting process; and a step of peeling the resist pattern from the substrate.
[10] A laminating step of forming the photosensitive resin laminate according to [4] above on a substrate that is a wafer on which circuit formation as an LSI has been completed,
An exposure step of exposing the photosensitive resin laminate;
A development step of removing a non-exposed portion of the photosensitive resin in the photosensitive resin laminate to form a resist pattern;
A method for manufacturing a semiconductor package, comprising: plating a substrate on which the resist pattern is formed; and peeling the resist pattern from the substrate.

  The present invention has excellent resistosso interface adhesion while maintaining good sensitivity and resolution, has a fine strip size when stripped with an alkaline aqueous solution of a photocured film, and has a waste liquid acid precipitation property (i.e., waste liquid treatability). Photosensitive resin composition that is good, photosensitive resin laminate using the photosensitive resin composition, method for forming a resist pattern on a substrate using the photosensitive resin laminate, and use of the resist pattern provide. The photosensitive resin laminate using the photosensitive resin composition of the present invention can be suitably used for the production of printed wiring boards, the production of lead frames, the production of semiconductor packages, the production of flat displays, and the like.

  Hereinafter, the present invention will be specifically described.

<Photosensitive resin composition>
The present invention relates to (a) a heat polymerized from a polymerization component containing an α, β-unsaturated carboxyl group-containing monomer and having an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000. 20 to 90% by mass of a plastic polymer (also referred to herein as “(a) thermoplastic polymer”), (b) an addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule ( A photosensitive resin composition comprising 3 to 75% by mass (also referred to as “(b) addition polymerizable monomer” in the present specification) and (c) 0.01 to 30% by mass of a photopolymerization initiator,
(A) As a thermoplastic polymer, (a-1) a polymer having a weight average molecular weight of 15,000 or more and 85,000 or less, and (a-2) a weight having a weight average molecular weight of 150,000 or more and 400,000 or less. A mass ratio (a-1) / (a-2) of the (a-1) polymer to the (a-2) polymer is 1 to 3, and Provided is a photosensitive resin composition in which the proportion of a copolymer containing an aromatic group as a polymerization component is 10% by mass or less.

(A) Thermoplastic polymer
(a) The thermoplastic polymer is polymerized from a polymerization component containing an α, β-unsaturated carboxyl group-containing monomer, and has an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000. A thermoplastic polymer. The carboxyl group in the α, β-unsaturated carboxyl group-containing monomer contributes to the fact that the photosensitive resin composition of the present invention has developability or releasability with respect to the developer or stripper comprising an alkaline aqueous solution. To do. The α, β-unsaturated carboxyl group-containing monomer is an α, β-unsaturated monomer from the viewpoint that a good resist laminate can be obtained.

  (A) The acid equivalent of a thermoplastic polymer is 100-600, Preferably it is 250-450. The acid equivalent is 100 or more from the viewpoint of ensuring compatibility with the solvent or other components in the photosensitive resin composition, particularly (b) the addition polymerizable monomer described later, and developability and releasability. From the viewpoint of maintaining, it is 600 or less. Here, the acid equivalent means the mass (gram) of the thermoplastic polymer having 1 equivalent of a carboxyl group therein. In addition, the acid equivalent in this specification is a value obtained by measuring with a 0.1 mol / L NaOH aqueous solution by potentiometric titration using a titration apparatus (for example, Hiranuma Reporting Titrator (COM-555)).

(A) The weight average molecular weight of the thermoplastic polymer is 5,000 to 500,000. The weight average molecular weight is 5,000 or more from the viewpoint of maintaining the thickness of the photosensitive resin laminate (that is, dry film resist) uniformly and obtaining resistance to the developer, and from the viewpoint of maintaining developability. 500,000 or less. Preferably, the weight average molecular weight is 20,000 to 300,000. The weight average molecular weight in this specification means the weight average molecular weight measured by gel permeation chromatography (GPC) using a calibration curve of polystyrene (for example, Shodex STANDARD SM-105 manufactured by Showa Denko KK). The weight average molecular weight can be typically measured using gel permeation chromatography (for example, 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

  (A) The thermoplastic polymer is one polymer or two or more copolymers of the first monomer described later, or one polymer of the second monomer described later. Or it is a 2 or more types of copolymer, or it is preferable that it is a copolymer of 1 or more types of this 1st monomer, and 1 or more types of this 2nd monomer.

  The first monomer is a carboxylic acid or carboxylic anhydride having one polymerizable unsaturated group in the molecule, such as (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, Mention may be made of maleic anhydride and maleic acid half esters. Among these, (meth) acrylic acid is particularly preferable from the viewpoint of developability with an alkaline solution. In the present specification, (meth) acryl means acryl or methacryl.

  The second monomer is non-acidic and has 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 ( Esters of vinyl alcohol such as (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, vinyl acetate , (Meth) acrylonitrile, styrene, and polymerizable styrene derivatives. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are particularly preferable from the viewpoint of image formability.

  (A) As a more specific example of a thermoplastic polymer, a polymer containing methyl methacrylate, methacrylic acid and styrene as a copolymerization component, methyl methacrylate, methacrylic acid and n-butyl acrylate as a copolymerization component And a polymer containing benzyl methacrylate, methyl methacrylate and 2-ethylhexyl acrylate as a copolymerization component.

  The thermoplastic polymer (a) contained in the photosensitive resin composition of the present invention is composed of (a-1) a polymer having a weight average molecular weight of 15,000 or more and 85,000 or less (in this specification, “(a -1) polymer ”) and (a-2) a polymer having a weight average molecular weight of 150,000 or more and 400,000 or less (also referred to as“ (a-2) polymer ”in the present specification). The mass ratio (a-1) / (a-2) of the (a-1) polymer to the (a-2) polymer must be 1 to 3. (A-1) The polymer is necessary for miniaturizing the resist pattern peeling piece, and (a-2) the polymer is the resist interface adhesion at the resist pattern (that is, the interface adhesion between the resist pattern and the substrate). ) To get enough. Moreover, if the said mass ratio (a-1) / (a-2) is 1 or more, a peeling piece will refine | miniaturize, and if it is 3 or less, the said suso interface adhesiveness is favorable. The mass ratio (a-1) / (a-2) is preferably 1 or more and 2.5 or less, and more preferably 1.5 or more and 2 or less.

  (A-1) The weight average molecular weight of the polymer is 15,000 or more, preferably 20,000 or more from the viewpoint of sso-interface adhesion, and is 85,000 or less from the viewpoint of making the peeled piece fine, 75,000 or less is preferable. (A-1) The polymer may be one type or two or more types.

  (A-1) The content of the polymer is preferably 30% by mass to 45% by mass of the total mass of (a) the thermoplastic polymer and (b) the addition polymerizable monomer. The content is preferably 30% by mass or more in order to make the peeled piece fine, and preferably 45% by mass or less in order to maintain the adhesion between the resist pattern and the substrate. The content is more preferably 30% by mass to 40% by mass, and still more preferably 33% by mass to 40% by mass.

  (A-2) The weight average molecular weight of the polymer is 150,000 or more, preferably 180,000 or more from the viewpoint of sso-interface adhesion, and is 400,000 or less from the viewpoint of peeling strip refinement, 300,000 or less is preferable. (A-2) The polymer may be one type or two or more types.

  (A-2) The content of the polymer is preferably 15% by mass to 30% by mass in the total mass of (a) the thermoplastic polymer and (b) the addition polymerizable monomer. The content is preferably 15% by mass or more in order to maintain the adhesion between the resist pattern and the substrate, and is preferably 30% by mass or less in order to make the release piece finer. The content is more preferably 15% by mass to 25% by mass, and still more preferably 17% by mass to 25% by mass.

  (A) The ratio of the copolymer which contains an aromatic group as a copolymerization component among thermoplastic polymers is 10 mass% or less with respect to the whole (a) thermoplastic polymer. It is necessary for the said ratio to be 10 mass% or less in order to obtain the favorable waste liquid processability by acid precipitation, More preferably, the said ratio is 8 mass% or less. On the other hand, it is preferable that the said ratio is 5 mass% or more from a viewpoint of reducing the scum aggregation in a image development process.

  Examples of the aromatic group of the copolymer component include an aryl (meth) acrylate (for example, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, cresyl (meth) acrylate, naphthyl (methacrylate), etc.), and a phenyl group. Vinyl compounds (eg styrene), benzyl (meth) acrylate, compounds having substituents such as alkoxy groups, halogens, alkyl groups on the aromatic ring of benzyl (meth) acrylate (eg methoxybenzyl (meth) acrylate, chlorobenzyl (meth)) Acrylate etc.). Among these, styrene and benzyl (meth) acrylate are particularly preferable from the viewpoint of obtaining good image formation.

  Content of the thermoplastic polymer (a) in the photosensitive resin composition of this invention is the range of 20-90 mass%, Preferably, it is the range of 25-70 mass%. The content is 20% by mass or more from the viewpoint of maintaining alkali developability, and is 90% by mass or less from the viewpoint that the resist pattern formed by exposure sufficiently exhibits the performance as a resist.

(B) Addition polymerizable monomer (b) The addition polymerizable monomer has at least one polymerizable ethylenically unsaturated bond in the molecule. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group from the viewpoint of good image forming properties. From the viewpoint of high resolution and edge fuse properties, the (b) addition polymerizable monomer includes the following general formula (I):

(Wherein R ₁ and R ₂ are each independently H or CH ₃ , and n ₁ , n ₂ and n ₃ are each independently an integer of 3 to 20).
And a photopolymerizable unsaturated compound represented by the following general formula (II):

Wherein R ₃ and R ₄ are each independently H or CH ₃ , A is C ₂ H ₄ , B is C ₃ H ₆ , and n ₄ and n ₅ are each independently 1 to 29 N ₄ + n ₅ is an integer of 2-30, n ₆ and n ₇ are each independently an integer of 0-29, and n ₆ + n ₇ is an integer of 0-30, and-(A- The arrangement of repeating units of O)-and-(B-O)-may be random or block. In the case of a block,-(A-O)-and-(B-O)- Any of these may be on the bisphenyl group side.)
It is preferable to contain 1 or more types selected from the group which consists of a photopolymerizable unsaturated compound represented by these.

In the compound represented by the general formula (I), R ₁ and R ₂ are each independently H or CH ₃ . N ₁ , n _2, and n ₃ are each independently 3 or more from the viewpoint of improving tenting properties, and are each independently 20 or less from the viewpoint of improving sensitivity and resolution. More preferably, n ₁ and n ₃ are each independently 3 or more and 10 or less, and n ₂ is 5 or more and 15 or less.

In the compound represented by the general formula (II), R ₃ and R ₄ are each independently H or CH ₃ . n ₄ and n ₅ are each independently 1 or more from the viewpoint of flexibility of the cured resist film, and are each 29 or less from the viewpoint of obtaining sufficient sensitivity. n ₄ + n ₅ is 2 or more from the viewpoint of tenting properties and 30 or less from the viewpoint of image forming properties. n ₆ and n ₇ are each independently 29 or less from the viewpoint of image formability. n ₆ + n ₇ is 30 or less from the viewpoint of development aggregation.

In the compound represented by the general formula (II), the value of n ₄ + n ₅ + n ₆ + n ₇ is 2 from the viewpoint of the flexibility and tenting property of a cured resist film obtained by curing the photosensitive resin composition. Preferably, it is preferably 40 or less from the viewpoint of the effect on resolution.

  Preferable specific examples of the unsaturated compound represented by the above general formula (I) include polyalkylene glycol dimethacrylate in which ethylene oxide is further added to both ends at an average of 3 moles on polypropylene glycol to which an average of 12 moles of propylene oxide is added. Is mentioned.

  As a preferable specific example of the unsaturated compound represented by the above general formula (II), polyethylene glycol dimethacrylate (NK, manufactured by Shin-Nakamura Chemical Co., Ltd.) having an average of 2 mol of ethylene oxide added to both ends of bisphenol A, respectively. Ester BPE-200) and polyethylene glycol dimethacrylate (NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.) with an average of 5 moles of ethylene oxide added to both ends of bisphenol A, and an average of 6 at each end of bisphenol A A polyalkylene glycol dimethacrylate added with 1 mol of ethylene oxide and an average of 2 mol of propylene oxide and a polyalkylene added with an average of 15 mol of ethylene oxide and an average of 2 mol of propylene oxide on both ends of bisphenol A, respectively. Dimethacrylate glycols and the like.

  (B) The proportion of the photopolymerizable unsaturated compound represented by the general formula (I) in the addition polymerizable monomer is 3% by mass from the viewpoint of improving sensitivity, resolution, adhesion and tenting properties. The above is preferable, and 70% by mass or less is preferable from the viewpoint of suppressing edge fuse. The ratio is more preferably 3 to 50% by mass, and still more preferably 3 to 30% by mass.

  (B) The proportion of the photopolymerizable unsaturated compound represented by the general formula (II) in the addition polymerizable monomer is preferably 3% by mass or more from the viewpoint of improving sensitivity, and edge fuse is suppressed. From the viewpoint of achieving the above, 70% by mass or less is preferable. The ratio is more preferably 10 to 65% by mass, and still more preferably 15 to 55% by mass.

  The addition polymerizable monomer (b) used in the photosensitive resin composition of the present invention includes at least one polymerizable ethylenically unsaturated bond other than the compounds represented by the general formulas (I) and (II). Known compounds having can be used. Examples of such compounds include 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxyhexaethylene glycol acrylate, and half ester compounds of phthalic anhydride and 2-hydroxypropyl acrylate. And propylene oxide reaction product (trade name OE-A 200, manufactured by Nippon Shokubai Chemical Co., Ltd.), 4-normal octylphenoxypentapropylene glycol acrylate, 1,6-hexanediol (meth) acrylate, 1,4-cyclohexanediol di ( (Meth) acrylate, and polyoxyalkylene glycol di (meth) acrylates such as polypropylene glycol di (meth) acrylate and polyethylene glycol di (meth) acrylate Relate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, 2,2-bis ( 4-methacryloxypentaethoxyphenyl) propane, polyfunctional (meth) acrylates containing urethane groups such as urethanates of hexamethylene diisocyanate and nonapropylene glycol monomethacrylate, and polyfunctional (meth) acrylates of isocyanuric acid ester compounds Is mentioned. These may be used alone or in combination of two or more.

  Content of (b) addition polymerizable monomer in the photosensitive resin composition of this invention is 3-75 mass%, More preferably, it is 5-75 mass%, More preferably, it is 15-70 mass%. is there. The content is 3% by mass or more from the viewpoint of suppressing poor curing of the photosensitive resin composition and development time delay, and 75% by mass from the viewpoint of suppressing cold flow and delay of peeling of the cured resist. It is as follows.

(C) Photopolymerization initiator (c) The photopolymerization initiator includes all those usually used as a photopolymerization initiator for photosensitive resins. In particular, from the viewpoint of obtaining good image formation, a hexaarylbisimidazole derivative (hereinafter also referred to as a triarylimidazolyl dimer) is preferably used. Examples of the triarylimidazolyl dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer (hereinafter referred to as 2,2′-bis (2-chlorophenyl) -4,4 ′, 5, 5'-tetraphenyl-1,1'-bisimidazole), 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-difluoromethylphenyl) -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-methoxyphene) L) -imidazolyl dimer, 2,2′-bis- (2,3,5-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer 2,2′-bis- (2,3,6-trifluorophenyl) -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 2,2′-bis- (2,3,4,6-tetrafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, and 2 2,2'-bis- (2,3,4,5,6-pentafluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer. In particular, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer is a photopolymerization initiator having a high effect on resolution and the strength of a cured resist film, and is preferably used. These may be used alone or in combination of two or more.

  (C) The inclusion of an acridine compound or a pyrazoline compound as a photopolymerization initiator is preferable from the viewpoint of obtaining high sensitivity. Examples of acridine compounds include acridine, 9-phenylacridine, 9- (4-tolyl) acridine, 9- (4-methoxyphenyl) acridine, 9- (4-hydroxyphenyl) acridine, 9-ethylacridine, 9-chloroethyl. Acridine, 9-methoxyacridine, 9-ethoxyacridine, 9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4-n -Butylphenyl) acridine, 9- (4-tert-butylphenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- (4-acetylphenyl) acridine, 9- (4-dimethylaminophenyl) acridine, 9 -(4-Chlorophenyl) acridine, 9- (4-bromophe L) acridine, 9- (3-methylphenyl) acridine, 9- (3-tert-butylphenyl) acridine, 9- (3-acetylphenyl) acridine, 9- (3-dimethylaminophenyl) acridine, 9- ( 3-diethylaminophenyl) acridine, 9- (3-chlorophenyl) acridine, 9- (3-bromophenyl) acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, 9- (4-pyridyl) ) Acridine. Of these, 9-phenylacridine is desirable from the viewpoint of obtaining good image quality.

  Examples of the pyrazoline compound include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, or 1- (4- (benzoxazol-2-yl). ) Phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl) -Phenyl) -pyrazoline and 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline are preferred.

  Examples of other photopolymerization initiators that can be used as the photopolymerization initiator (c) include 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, and 3- Quinones such as chloro-2-methylanthraquinone, benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], and aromatic ketones such as 4,4′-bis (diethylamino) benzophenone, benzoin, benzoinethyl Ether, benzoinphenyl Benzoin ethers such as ether, methylbenzoin and ethylbenzoin, benzyl dimethyl ketal, benzyl diethyl ketal, combinations of thioxanthones and alkylaminobenzoic acid, and 1-phenyl-1,2-propanedione-2-O- Examples include oxime esters such as benzoin oxime and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime.

  Examples of the combination of the above thioxanthones and alkylaminobenzoic acid include, for example, a combination of ethylthioxanthone and ethyl dimethylaminobenzoate, a combination of 2-chlorothioxanthone and dimethylaminobenzoic acid, and isopropylthioxanthone and dimethyl. A combination with ethyl aminobenzoate is mentioned. Further, N-aryl amino acids may be used in place of the alkylaminobenzoic acid. Examples of N-aryl amino acids include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. Among these, N-phenylglycine is particularly preferable.

  Content of the (c) photoinitiator in the photosensitive resin composition is 0.01-30 mass%, Preferably it is 0.05-10 mass%. The above content is 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity at the time of photopolymerization by exposure, and light is applied to the bottom surface of the photosensitive resin composition (that is, a portion far from the light source) at the time of photopolymerization. It is 30% by mass or less from the viewpoint of sufficiently transmitting and obtaining good resolution and adhesion.

Other Components The photosensitive resin composition of the present invention can contain various additives as other components of the components (a) to (c). Specifically, for example, coloring substances such as dyes and pigments, color forming dyes, stabilizers, plasticizers, and the like can be employed.

  Examples of the coloring substance include phthalocyanine green, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, basic blue 20, and diamond green.

  The coloring dye can be contained in the photosensitive resin composition for the purpose of giving a visible image upon exposure. Examples of coloring dyes include leuco dyes or combinations of fluorane dyes and halogen compounds. 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, and chlorinated triazine compounds. .

  The content of the coloring substance and the color forming dye in the photosensitive resin composition is preferably 0.01 to 10% by mass. The content is preferably 0.01% by mass or more from the viewpoint of obtaining good colorability and color developability, good contrast between the exposed area and the unexposed area, and good storage stability. 10 mass% or less is preferable from a point.

  Furthermore, in order to improve the thermal stability or storage stability of the photosensitive resin composition, as a stabilizer, the photosensitive resin composition includes a radical polymerization inhibitor, a benzotriazole, and a carboxybenzotriazole. It is preferable to contain one or more selected compounds.

  Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis. (4-Methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine.

  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, and 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 content of the stabilizer in the photosensitive resin composition, in particular, the total content of radical polymerization inhibitors, benzotriazoles and carboxybenzotriazoles is preferably 0.01 to 3% by mass, more preferably 0. 0.05 to 1% by mass. The content is preferably 0.01% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and is preferably 3% by mass or less from the viewpoint of maintaining good exposure sensitivity. .

  Examples of the plasticizer include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, Glycol esters such as polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, phthalates such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, Triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate And the like.

  It is preferable that content of the plasticizer in the photosensitive resin composition is 5-50 mass%, More preferably, it is 5-30 mass%. The content is preferably 5% by mass or more from the viewpoint of suppressing development time delay and imparting flexibility to the cured resist film, and is preferably 50% by mass or less from the viewpoint of suppressing insufficient curing and cold flow. .

<Photosensitive resin composition preparation solution>
The photosensitive resin composition of the present invention can also be used for various applications in the form of a photosensitive resin composition preparation liquid to which a solvent is added. Suitable solvents include ketones represented by methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol and isopropyl alcohol. It is preferable to adjust the amount of the solvent to be added to the photosensitive resin composition so that the solution viscosity of the photosensitive resin composition preparation liquid measured with an E-type viscometer is 500 to 4000 mPa · sec at 25 ° C. .

<Photosensitive resin laminate>
The present invention also provides a photosensitive resin laminate in which the photosensitive resin composition of the present invention as described above is laminated on a support. The photosensitive resin laminate may have a protective layer on the surface of the layer made of the photosensitive resin composition (hereinafter also referred to as photosensitive resin layer) opposite to the support.

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

  When forming a protective layer in a photosensitive resin laminate, an important characteristic of the protective layer is that the protective layer is sufficiently smaller than the support in terms of adhesion to the photosensitive resin layer, and the protective layer can be easily peeled off. It is. From the above viewpoint, for example, a polyethylene film and a polypropylene film can be preferably used as the protective layer. Moreover, the film excellent in peelability shown by Unexamined-Japanese-Patent No. 59-202457 can also be used preferably. As a film thickness of a protective layer, 10-100 micrometers is preferable and 10-50 micrometers is more preferable.

  The thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably 5 to 100 μm, and more preferably 7 to 60 μm. The thinner the photosensitive resin layer, the better the resolution, and the thicker the film strength, the more suitable the film thickness can be selected according to the application.

  As a method for producing the photosensitive resin laminate of the present invention by sequentially laminating a support, a photosensitive resin layer, and if necessary, a protective layer, a conventionally known method can be employed.

  For example, the above-mentioned photosensitive resin composition preparation liquid is prepared using the photosensitive resin composition of the present invention, and this is first coated on a support using a bar coater or a roll coater, dried, and supported. A photosensitive resin layer made of the photosensitive resin composition is laminated on the body. Next, a protective layer is laminated on the photosensitive resin layer as necessary. The photosensitive resin laminated body can be produced by the above.

<Resist pattern formation method>
The present invention also provides a resist pattern forming method using the above-described photosensitive resin laminate of the present invention. The resist pattern forming method includes a laminating step of forming the photosensitive resin laminate on a substrate, an exposure step of exposing the photosensitive resin laminate, and an unexposed portion of the photosensitive resin in the photosensitive resin laminate. And a developing step of forming a resist pattern by removing the resist pattern. A specific example of the resist forming method will be described below.

  First, in the laminating process, a photosensitive resin laminate is formed on a substrate using, for example, a laminator. When 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 on only one surface of the substrate surface, or may be laminated on both surfaces as necessary. The heating temperature at this time is generally 40 to 160 ° C. Moreover, when performing this thermocompression bonding twice or more, since the adhesiveness with respect to the board | substrate of the resist pattern obtained improves, it is preferable. At this time, a two-stage laminator equipped with two rolls may be used for pressure bonding, or pressure bonding may be performed by repeatedly passing the photosensitive resin laminate and the substrate through the roll.

  Next, in the exposure step, the photosensitive resin laminate is exposed using an exposure machine. If necessary, the support can be peeled off and exposed to the photosensitive resin laminate with active light through a photomask. The exposure amount is appropriately determined from the light source illuminance and the exposure time, and may be measured using a light meter.

  In the exposure step, a maskless exposure method may be used. Maskless exposure is a method in which exposure is performed directly on a substrate by a drawing apparatus 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 can be used. The drawing pattern is controlled by a computer. The exposure amount of maskless exposure is appropriately determined by the illuminance of the exposure light source and the moving speed of the substrate.

Next, in the developing step, the unexposed portion of the photosensitive resin in the photosensitive resin laminate is removed using a developing device. Specifically, if there is a support on the photosensitive resin layer after the above exposure, this is excluded. Subsequently, an unexposed portion of the photosensitive resin is developed and removed using a developer composed of an alkaline aqueous solution to obtain a resist pattern. As the alkaline aqueous solution, an aqueous solution such as Na ₂ CO ₃ or K ₂ CO ₃ is preferable. The developer is selected in accordance with the characteristics of the photosensitive resin layer, and an aqueous Na ₂ CO ₃ solution having a concentration of 0.2 to 2% by mass is generally used. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed. In addition, it is preferable to maintain the temperature of this developing solution in a development process at the constant temperature in the range of 20-40 degreeC.

  Although a resist pattern is obtained by the above-mentioned process, depending on the case, a 100-300 degreeC heating process can also be performed after a image development process. By carrying out this heating step, the chemical resistance of the resist pattern can be further improved. For heating, a heating furnace such as hot air, infrared rays, or far infrared rays can be used.

<Conductor Pattern Manufacturing Method and Printed Wiring Board Manufacturing Method>
The present invention also provides a method for producing a conductor pattern using the above-mentioned photosensitive resin laminate, and a method for producing a printed wiring board using the above-mentioned photosensitive resin laminate. In the method for producing a conductor pattern, the above-described photosensitive resin laminate of the present invention is exposed on a photosensitive resin laminate, a laminating step for forming a metal plate or a metal film insulating plate on a substrate that is a copper clad laminate, for example. An exposure step, a development step of removing a non-exposed portion of the photosensitive resin in the photosensitive resin laminate to form a resist pattern, and a substrate on which the resist pattern is formed (for example, the copper surface of the substrate in a copper-clad laminate) A step of forming a conductor pattern by etching or plating. In the laminating step, the exposing step and the developing step, the same methods and conditions as described above in the resist pattern forming method can be preferably employed.

  Moreover, the manufacturing method of a printed wiring board is the exposure process which exposes the photosensitive resin laminated body of this invention mentioned above on the board | substrate which is a copper clad laminated board or a flexible substrate, and the photosensitive resin laminated body, It includes a developing step of removing a non-exposed portion of the photosensitive resin in the photosensitive resin laminate to form a resist pattern, a step of etching or plating a substrate on which the resist pattern is formed, and a step of peeling the resist pattern from the substrate. . Typically, after performing the laminating step, the exposing step and the developing step under the same method and conditions as described above in the resist pattern forming method, the exposed substrate is etched by a known method such as an etching method or a plating method. Further, a desired printed wiring board can be obtained by performing a peeling step of peeling the resist pattern from the substrate with an aqueous solution having alkalinity stronger than that of the developer. The alkaline aqueous solution for peeling (hereinafter also referred to as “peeling solution”) is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of 2 to 5% by mass is generally used. It is possible to add a small amount of a water-soluble solvent to the stripping solution. In addition, it is preferable that the temperature of this peeling liquid in a peeling process is the range of 40-70 degreeC.

<Lead frame manufacturing method>
The present invention also provides a method for producing a lead frame using the above-described photosensitive resin laminate of the present invention. The method includes a lamination step of forming the above-described photosensitive resin laminate of the present invention on a substrate that is a metal plate, an exposure step of exposing the photosensitive resin laminate, and unexposed photosensitive resin in the photosensitive resin laminate. It includes a developing step of removing the exposed portion to form a resist pattern, a step of etching the substrate on which the resist pattern is formed, and a step of peeling the resist pattern from the substrate. Typically, using a metal plate such as copper, a copper alloy, or an iron-based alloy as a substrate, the laminating step, the exposing step, and the developing step were performed under the same method and conditions as described above in the resist pattern forming method. Thereafter, a step of etching the exposed substrate to form a conductor pattern is performed. Thereafter, a desired lead frame can be obtained by performing a peeling process in which the resist pattern is peeled by the same method as the above-described printed wiring board manufacturing method.

<Manufacturing method of substrate having uneven pattern>
The present invention also provides a method for producing a substrate having a concavo-convex pattern using the above-described photosensitive resin laminate. The method includes a laminating step of forming a photosensitive resin laminate on a substrate, an exposure step of exposing the photosensitive resin laminate, and removing an unexposed portion of the photosensitive resin in the photosensitive resin laminate to form a resist pattern. A development step to form, a step of sandblasting the substrate on which the resist pattern is formed, and a step of peeling the resist pattern from the substrate. In the laminating step, the exposing step and the developing step, the same methods and conditions as described above in the resist pattern forming method can be preferably employed. The resist pattern formed in the manufacturing method of this board | substrate can be used as a protective mask member at the time of processing a board | substrate with a sandblasting method.

As the substrate, glass, a silicon wafer, amorphous silicon, polycrystalline silicon, ceramic, sapphire, a metal material, or the like can be used in addition to a glass substrate coated with a glass rib paste. Typically, a resist pattern is formed on a substrate coated with a glass rib paste by performing a laminating process, an exposing process, and a developing process by the same method as the resist pattern forming method described above. After that, a blasting material is sprayed on the formed resist pattern to be cut to a desired depth, and a resist pattern portion remaining on the substrate is removed from the substrate with an alkali stripping solution or the like, and then on the substrate. A substrate having a fine uneven pattern can be formed. As the blasting material used in the sand blasting process, known materials are used. For example, fine particles having a particle diameter of about 2 to 100 μm such as SiC, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO, glass, stainless steel and the like are used.

<Semiconductor package manufacturing method>
The present invention also provides a method of manufacturing a semiconductor package using the above-described photosensitive resin laminate. The method includes the above-described photosensitive resin laminate of the present invention formed on a substrate that is a wafer on which circuit formation as LSI has been completed, an exposure step of exposing the photosensitive resin laminate, and a photosensitive resin laminate. A development step of removing a non-exposed portion of the photosensitive resin in the body to form a resist pattern, a step of plating a substrate on which the resist pattern is formed, and a step of peeling the resist pattern from the substrate. Typically, after performing the laminating step, the exposing step and the developing step under the same method and conditions as described above in the resist pattern forming method, the exposed opening is subjected to columnar plating such as copper and solder, A step of forming a conductor pattern is performed. Thereafter, a peeling process for peeling the resist pattern by the same method as the printed wiring board manufacturing method described above is performed, and further, a thin metal layer other than the columnar plating is removed by etching, thereby obtaining a desired semiconductor. You can get a package.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. A method for producing samples for evaluation of Examples and Comparative Examples, an evaluation method for the obtained samples, and an evaluation result will be described below.

1. Production of Evaluation Samples The photosensitive resin laminates in Examples and Comparative Examples were produced as follows.

<Preparation of photosensitive resin laminate>
A photosensitive resin having a composition shown in Table 1 and a composition ratio shown in Table 2 (the numerical values in Table 2 are parts by mass, and P-1 to P-5 indicate solid amounts not containing a solvent). The composition is thoroughly stirred and mixed, and uniformly applied to the surface of a 16 μm-thick polyethylene terephthalate film as a support using a bar coater, and dried in a dryer at 95 ° C. for 4 minutes to form a photosensitive resin layer. did. The thickness of the photosensitive resin layer was 45 μm.

  In the compositions shown in Tables 1 and 2, MEK represents methyl ethyl ketone, and the mass parts in the composition ratio of compounds other than MEK are values not including MEK.

  Next, a 22 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.

<Board surface preparation>
As a substrate for evaluation of sensitivity, resolution, and adhesion, a 1.2 mm thick copper clad laminate in which a 35 μm thick rolled copper foil was laminated, and the surface was wet buffol polished (manufactured by 3M Co., Ltd., Scotch Bright). (Registered trademark) HD # 600 was used twice).

  The substrate for evaluation was prepared by jet scrub polishing (manufactured by Nippon Grinding Abrasive Co., Ltd., using Sac Random A (registered trademark) # F220P) at a spray pressure of 0.20 MPa.

<Laminate>
Using a hot roll laminator (Asahi Kasei Co., Ltd., AL-700) on the copper clad laminate preheated to 60 ° C. after the above-mentioned substrate leveling while peeling the polyethylene film of the photosensitive resin laminate, roll temperature Lamination was performed at 105 ° C. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.

<Exposure>
A mask film necessary for the evaluation of the photosensitive resin layer is placed on a polyethylene terephthalate film as a support, and an ultra-high pressure mercury lamp (manufactured by Oak Manufacturing Co., Ltd., HMW-201KB) is used to make a 21-step tablet made by Stöffer with 7 steps. The exposure amount was as follows.

<Development>
After the polyethylene terephthalate film is peeled off, a 1 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. is sprayed for a predetermined time using an alkali developing machine (produced by Fuji Kiko Co., Ltd., a dry film developing machine), and an unexposed portion of the photosensitive resin layer Was dissolved and removed in a time twice the minimum image time. 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.

2. Evaluation Method (1) Sensitivity Evaluation 15 minutes after laminating using the above-mentioned evaluation substrate, photosensitivity was obtained using a 21-step tablet manufactured by Stofer, whose lightness was changed from transparent to black in 21 steps. The resin layer was exposed. After exposure, the film was developed with a development time twice as long as the minimum development time, and the number of step tablet stages in which the resist film remained completely was defined as the sensitivity value.

(2) Resolution Evaluation After the lamination using the evaluation substrate, the photosensitive resin layer was passed through a line pattern mask having a ratio of 1: 1 between the exposed part and the unexposed part. Exposed. Development was performed with a development time twice as long as the minimum development time, and the minimum mask width in which a cured resist line was normally formed was defined as an evaluation value of resolution, and the resolution was ranked as follows.
A: The resolution value is 45 μm or less.
○: The resolution value exceeds 45 μm and is 55 μm or less.
Δ: The resolution value exceeds 55 μm.

(3) Adhesion evaluation After the lamination using the substrate for evaluation, 15 minutes have passed, and the photosensitive resin layer is exposed through a line pattern mask in which the width of the exposed portion and the unexposed portion is 1: 1. did. Development was performed with a development time twice as long as the minimum development time, and the minimum mask line width in which a cured resist line was normally formed was defined as an evaluation value for adhesion.
A: Adhesion value is 45 μm or less.
○: Adhesion value exceeds 45 μm and is 55 μm or less.
(Triangle | delta): The value of adhesiveness exceeds 55 micrometers.

(4) Evaluation of resist stripping piece After laminating using the substrate for evaluation, 15 minutes passed, and the photosensitive resin layer was exposed through a mask having a pattern of 6 cm × 6 cm. After developing with a development time twice as long as the minimum development time, the resist was immersed in a 3% by mass aqueous caustic soda solution at 50 ° C., and the shape of the resist cured film peeled off from the substrate (peeled piece shape) was evaluated as follows.
◯: When the cured film is peeled off from the substrate, a large number of cracks are generated and peeled off, and then a fine piece having a long side of less than about 5 mm is formed.
(Triangle | delta): When a cured film peels from a board | substrate, after a crack arises and peels, it becomes a strip with a long side about 5 mm or more and less than 10 mm.
X: When a cured film peels from a board | substrate, after a crack arises and peels, it becomes a shape whose long side is about 10 mm or more.

(5) Sole interface adhesion Suse adhesion at the interface between the resist and the substrate is determined by a scanning electron microscope (SEM) at the tip of a 45 μm line where the width of the exposed area and the unexposed area is 1: 1. The adhesion between the substrate and the substrate was observed and evaluated according to the following criteria.
○: The end of the line is completely adhered.
Δ: A part of the end of the line is floating.
X: The tip is completely lifted.

(6) Waste liquid processability The resist for evaluation was produced according to the preparation method of the photosensitive resin laminated body mentioned above. A developer (ii) in which an unexposed resist is completely dissolved in 200 mL of a 1% by mass Na ₂ CO ₃ aqueous solution at a throughput of 0.4 m ² / L, and an ultrahigh pressure mercury lamp in 200 mL of a 3% by mass NaOH aqueous solution. (Oak Seisakusho, HMW-201KB) was prepared by stirring the resist exposed at a dose of 7 steps by a 21-step tablet made by Stöffer at a throughput of 1.0 m ² / L and stirring at 50 ° C. for 3 hours. The stripping solution (b) was mixed in a beaker having an outer diameter of 80 mm, and 60% by mass sulfuric acid was added dropwise with stirring at 35 ° C. to adjust to pH 3. After the stirring was stopped, evaluation was performed as follows.
○: The precipitate becomes 30% or less of the total liquid height 30 minutes after the stirring is stopped, and the supernatant becomes transparent.
Δ: 30 minutes after stopping stirring, the precipitate becomes more than 30% and 50% or less of the total liquid height, and the supernatant becomes transparent.
X: In 30 minutes after stopping stirring, the precipitate exceeds 50% of the total liquid height, or the supernatant is cloudy.

3. Evaluation results Table 2 shows the evaluation results of Examples and Comparative Examples.

  The present invention includes the manufacture of printed wiring boards, the manufacture of lead frames for IC chip mounting, the precision processing of metal foils such as the manufacture of metal masks, the manufacture of packages such as BGA and CSP, the manufacture of tape substrates such as COF and TAB, the production of semiconductor bumps It can be suitably applied to manufacturing, manufacturing of ITO electrodes and address electrodes, manufacturing of partition walls of flat panel displays such as electromagnetic wave shields, and the like.

Claims (10)

(A) Thermoplastic polymer 20 having an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000, polymerized from a polymerization component containing an α, β-unsaturated carboxyl group-containing monomer ~ 90% by mass, (b) 3 to 75% by mass of an addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule, and (c) 0.01 to 30% by mass of a photopolymerization initiator. A photosensitive resin composition comprising:
(A) As a thermoplastic polymer, (a-1) a polymer having a weight average molecular weight of 15,000 or more and 85,000 or less, and (a-2) a weight having a weight average molecular weight of 150,000 or more and 400,000 or less. A mass ratio (a-1) / (a-2) of the (a-1) polymer to the (a-2) polymer is 1 to 3, and among the polymers, The photosensitive resin composition whose ratio of the copolymer containing an aromatic group as a polymerization component is 10 mass% or less.   The photosensitive resin composition of Claim 1 which contains a hexaarylbisimidazole derivative as said (c) photoinitiator. As the addition polymerizable monomer (b) having at least one polymerizable ethylenically unsaturated bond in the molecule, the following general formula (I):

(Wherein R ₁ and R ₂ are each independently H or CH ₃ , and n ₁ , n ₂ and n ₃ are each independently an integer of 3 to 20).
And a photopolymerizable unsaturated compound represented by the following general formula (II):

Wherein R ₃ and R ₄ are each independently H or CH ₃ , A is C ₂ H ₄ , B is C ₃ H ₆ , and n ₄ and n ₅ are each independently 1 to 29 N ₄ + n ₅ is an integer of 2-30, n ₆ and n ₇ are each independently an integer of 0-29, and n ₆ + n ₇ is an integer of 0-30, and-(A- The arrangement of repeating units of O)-and-(B-O)-may be random or block. In the case of a block,-(A-O)-and-(B-O)- Any of these may be on the bisphenyl group side.)
The photosensitive resin composition of Claim 1 or 2 containing 1 or more types selected from the group which consists of a photopolymerizable unsaturated compound represented by these.   The photosensitive resin laminated body by which the photosensitive resin composition of any one of Claims 1-3 is laminated | stacked on a support body. A laminating step for forming the photosensitive resin laminate according to claim 4 on a substrate,
A resist pattern forming method comprising: an exposure step of exposing the photosensitive resin laminate; and a developing step of removing a non-exposed portion of the photosensitive resin in the photosensitive resin laminate to form a resist pattern. A laminating step of forming the photosensitive resin laminate according to claim 4 on a substrate which is a metal plate or a metal film insulating plate,
An exposure step for exposing the photosensitive resin laminate;
A developing step of removing a non-exposed portion of the photosensitive resin in the photosensitive resin laminate to form a resist pattern; and a step of forming a conductor pattern by etching or plating the substrate on which the resist pattern is formed. The manufacturing method of a conductor pattern. A laminating step of forming the photosensitive resin laminate according to claim 4 on a substrate which is a copper clad laminate or a flexible substrate,
An exposure step for exposing the photosensitive resin laminate;
A developing step of forming a resist pattern by removing an unexposed portion of the photosensitive resin in the photosensitive resin laminate,
A method for manufacturing a printed wiring board, comprising: a step of etching or plating a substrate on which the resist pattern is formed; and a step of peeling the resist pattern from the substrate. A laminating step of forming the photosensitive resin laminate according to claim 4 on a substrate that is a metal plate,
An exposure step for exposing the photosensitive resin laminate;
A developing step of forming a resist pattern by removing an unexposed portion of the photosensitive resin in the photosensitive resin laminate,
A method of manufacturing a lead frame, comprising: etching a substrate on which the resist pattern is formed; and peeling the resist pattern from the substrate. A laminating step for forming the photosensitive resin laminate according to claim 4 on a substrate,
An exposure step for exposing the photosensitive resin laminate;
A developing step of forming a resist pattern by removing an unexposed portion of the photosensitive resin in the photosensitive resin laminate,
A method for manufacturing a substrate having a concavo-convex pattern, comprising: a step of sandblasting a substrate on which the resist pattern is formed; and a step of peeling the resist pattern from the substrate. A laminating step of forming the photosensitive resin laminate according to claim 4 on a substrate which is a wafer on which circuit formation as LSI has been completed,
An exposure step for exposing the photosensitive resin laminate;
A developing step of forming a resist pattern by removing an unexposed portion of the photosensitive resin in the photosensitive resin laminate,
A method for manufacturing a semiconductor package, comprising: plating a substrate on which the resist pattern is formed; and peeling the resist pattern from the substrate.