JP5570275B2 - Dry film resist roll - Google Patents

Description

  The present invention relates to a dry film resist roll which is a photosensitive resin laminate formed by laminating a photosensitive resin layer developable with an alkaline aqueous solution on a support, and a resist pattern is formed on a substrate using the dry film resist roll. And a use of the resist pattern.

  More specifically, 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 (hereinafter also referred to as lead frames), the metal foil precision processing such as the manufacture of metal masks, BGA ( Tape represented by ball grid array), semiconductor package manufacturing such as CSP (chip size package), TAB (Tape Automated Bonding), COF (Chip On Film: semiconductor IC mounted on a film-like fine wiring board) The present invention relates to a dry film resist roll that provides a resist pattern suitable for manufacturing a substrate, manufacturing a semiconductor bump, manufacturing an ITO electrode, an address electrode, or an electromagnetic wave shield member in the field of flat panel displays.

  Conventionally, a photolithography method has been widely used in applications such as printed wiring boards. The photolithographic method is a method in which a photosensitive resin composition is applied onto a substrate, subjected to pattern exposure, an exposed portion of the photosensitive resin composition is polymerized and cured, and an unexposed portion is removed with a developer, or The exposed portion is solubilized and removed with a developer to form a resist pattern on the substrate, and after etching or plating to form a conductor pattern, the resist pattern is peeled off from the substrate. This refers to a method of forming a conductor pattern on a substrate.

  In the above photolithography method, usually, when the photosensitive resin composition is applied onto the substrate, a solution of the photosensitive resin composition is applied to the substrate and dried, or the support, the photosensitive resin composition A method of laminating a layer made of the above (hereinafter also referred to as “photosensitive resin layer”) and a photosensitive resin laminate (hereinafter also referred to as “dry film resist”) in which protective layers are sequentially laminated as necessary 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, the protective layer of the dry film resist 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 (made of polyethylene terephthalate, etc.) are in this order. . In addition, some laminating methods include a temporary attachment process. In this case, first, the temporary block is lowered to the substrate while the support and the photosensitive resin layer are adsorbed to the temporary block by vacuum suction, and the photosensitive resin layer is temporarily bonded to the substrate. Next, after the vacuum is released, the temporary block is lifted, and at the same time when the support and the photosensitive resin layer are separated from the temporary block, the laminate roll comes down and lamination begins. Next, the exposed portion is polymerized and cured by exposing the photosensitive resin layer with ultraviolet rays such as i rays (365 nm) emitted from an ultrahigh pressure mercury lamp through a photomask having a wiring pattern. Next, the support 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. For the etching process, for example, cupric chloride, ferric chloride, and a copper ammonia complex solution are used. Finally, the resist pattern is peeled from the substrate with an alkaline aqueous solution such as sodium hydroxide to produce a substrate having a conductor pattern, that is, a printed wiring board.

  Here, as a protective layer for a dry film resist, for example, Patent Document 1 describes that an effect of reducing laminating properties and reducing air voids can be obtained by using a polypropylene film for the protective layer. Patent Document 2 describes the sensitivity stability due to the protective layer having a low oxygen permeability.

JP 2001-290278 A JP 2005-74632 A

  With the recent miniaturization of wiring intervals in printed wiring boards, the demand for high resolution is increasing for dry film resists. Low molecular weight photopolymerizable monomers are often used to provide high resolution. However, when the protective layer is a general polyethylene film, if a large amount of low molecular weight monomer is used, the monomer in the photosensitive resin layer passes through the protective layer (hereinafter referred to as bleed out), and the protective layer is wound up. The problem of soiling the roll occurs. In many cases, the dry film resist is a roll product. In this case, since the protective layer and the support are in contact with each other, the monomer passing through the protective layer is transferred to the surface of the support and becomes sticky. The support becomes difficult to peel off from the attachment block, which may cause a laminate failure. In particular, when a smoother support body with less lubricant is used, slippage from the temporary block is poor, and such temporary defective attachment due to bleeding out becomes serious. On the other hand, such a highly smooth support is often necessary for forming a fine resist pattern. However, none of the above-mentioned patent documents considers the problem of suppression of the bleed-out related to the protective layer.

  The present invention provides a resist pattern with high resolution adhesion (that is, adhesion at the time of forming a micropattern) by suppressing bleed-out of the monomer in the photosensitive resin from the protective layer and thereby suppressing temporary attachment failure. It is an object of the present invention to provide a dry film resist roll, a method for forming a resist pattern on a substrate using the dry film resist roll, and a use of the resist pattern.

（式中、Ｒ₁及びＲ₂は各々独立にＨ又はＣＨ₃であり、ｎ₁、ｎ₂及びｎ₃は各々独立に３〜２０の整数である。）
又は下記一般式（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を含有する、上記［１］〜［３］のいずれかに記載のドライフィルムレジストロール。
［５］ 上記［１］〜［４］のいずれかに記載のドライフィルムレジストロールを用いて、基板上に感光性樹脂層を形成するラミネート工程、
該感光性樹脂層を露光する露光工程、及び
該露光後の感光性樹脂層を現像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［１］〜［４］のいずれかに記載のドライフィルムレジストロールを用いて、金属板又は金属皮膜絶縁板である基板上に感光性樹脂層を形成するラミネート工程、
該感光性樹脂層を露光する露光工程、
該露光後の感光性樹脂層を現像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導体パターン形成工程
を含む、導体パターンの製造方法。
［７］ 上記［１］〜［４］のいずれかに記載のドライフィルムレジストロールを用いて、銅張積層板又はフレキシブル基板である基板上に感光性樹脂層を形成するラミネート工程、
該感光性樹脂層を露光する露光工程、
該露光後の感光性樹脂層を現像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し、次いでレジストパターンを剥離する配線形成工程
を含む、プリント配線板の製造方法。
［８］ 上記［１］〜［４］のいずれかに記載のドライフィルムレジストロールを用いて、金属板である基板上に感光性樹脂層を形成するラミネート工程、該感光性樹脂層を露光する露光工程、該露光後の感光性樹脂層を現像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し、次いでレジストパターンを剥離するリードフレーム形成工程を含む、リードフレームの製造方法。
［９］ 上記［１］〜［４］のいずれかに記載のドライフィルムレジストロールを用いて、基板上に感光性樹脂層を形成するラミネート工程、該感光性樹脂層を露光する露光工程、該露光後の感光性樹脂層を現像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工法によって加工し、次いでレジストパターンを剥離する凹凸パターン形成工程、を含む、凹凸パターンを有する基材の製造方法。
［１０］ 上記［１］〜［４］のいずれかに記載のドライフィルムレジストロールを用いて、ＬＳＩとしての回路形成が終了したウェハである基板上に感光性樹脂層を形成するラミネート工程、該感光性樹脂層を露光する露光工程、該露光後の感光性樹脂層を現像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し、次いでレジストパターンを剥離するパッケージ形成工程を含む、半導体パッケージの製造方法。 The above object can be achieved by the following configuration of the present invention.
[1] A dry film resist roll in which a photosensitive resin laminate is wound around a winding core,
The photosensitive resin laminate has a support (A), a photosensitive resin layer (B), and a protective layer (C) so as to be positioned in this order,
The photosensitive resin layer (B) is (a) 20 to 90% by mass of a thermoplastic polymer containing a carboxyl group, and (b) addition polymerizable having at least one polymerizable ethylenically unsaturated bond in the molecule. Including 5 to 75% by weight of monomer, and (c) 0.01 to 30% by weight of a photopolymerization initiator,
The free volume of the protective layer (C) is less than 0.2 nm ³ ;
A dry film resist roll having an internal pressure applied to the winding core of 0.1 MPa or more.
[2] A dry film resist roll in which a photosensitive resin laminate is wound around a winding core,
The photosensitive resin laminate has a support (A), a photosensitive resin layer (B), and a protective layer (C) so as to be positioned in this order,
The photosensitive resin layer (B) is (a) 20 to 90% by mass of a thermoplastic polymer containing a carboxyl group, and (b) addition polymerizable having at least one polymerizable ethylenically unsaturated bond in the molecule. Including 5 to 75% by weight of monomer, and (c) 0.01 to 30% by weight of a photopolymerization initiator,
The protective layer (C) is a polypropylene film,
A dry film resist roll having an internal pressure applied to the winding core of 0.1 MPa or more.
[3] The above [1] or [3], wherein the surface roughness (Ra) of the surface of the support (A) on the side opposite to the photosensitive resin layer (B) side is 0.001 to 0.06 μm. 2].
[4] As an addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule (b), the following general formula (I):

(In the formula, 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 3-20.)
Or 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 dry film resist roll in any one of said [1]-[3] containing the photopolymerizable unsaturated compound represented by these.
[5] A laminating step of forming a photosensitive resin layer on a substrate using the dry film resist roll according to any one of [1] to [4],
A resist pattern forming method, comprising: an exposure step of exposing the photosensitive resin layer; and a developing step of developing the exposed photosensitive resin layer to form a resist pattern.
[6] A laminating step of forming a photosensitive resin layer on a substrate that is a metal plate or a metal film insulating plate using the dry film resist roll according to any one of [1] to [4],
An exposure step of exposing the photosensitive resin layer;
A method for producing a conductor pattern, comprising: a developing step for developing the exposed photosensitive resin layer to form a resist pattern; and a conductor pattern forming step for etching or plating a substrate on which the resist pattern is formed.
[7] A laminating step of forming a photosensitive resin layer on a substrate that is a copper-clad laminate or a flexible substrate using the dry film resist roll according to any one of [1] to [4],
An exposure step of exposing the photosensitive resin layer;
A printed wiring board comprising: a developing step of developing the exposed photosensitive resin layer to form a resist pattern; and a wiring forming step of etching or plating the substrate on which the resist pattern is formed and then peeling the resist pattern Manufacturing method.
[8] Using the dry film resist roll according to any one of [1] to [4] above, a laminating step of forming a photosensitive resin layer on a substrate that is a metal plate, and exposing the photosensitive resin layer A lead frame comprising: an exposure step; a development step of developing the exposed photosensitive resin layer to form a resist pattern; a lead frame forming step of etching the substrate on which the resist pattern is formed and then peeling off the resist pattern Manufacturing method.
[9] Using the dry film resist roll according to any one of [1] to [4] above, a laminating process for forming a photosensitive resin layer on a substrate, an exposure process for exposing the photosensitive resin layer, A concavo-convex pattern comprising a development step of developing a photosensitive resin layer after exposure to form a resist pattern, a concavo-convex pattern forming step of processing the substrate on which the resist pattern is formed by a sandblasting method, and then peeling the resist pattern The manufacturing method of the base material which has this.
[10] A laminating step of forming a photosensitive resin layer on a substrate that is a wafer on which circuit formation as an LSI has been completed, using the dry film resist roll according to any one of [1] to [4], An exposure process for exposing the photosensitive resin layer, a development process for developing the exposed photosensitive resin layer to form a resist pattern, and a package formation for plating the substrate on which the resist pattern is formed and then peeling the resist pattern A manufacturing method of a semiconductor package including a process.

  ADVANTAGE OF THE INVENTION According to this invention, since the bleed-out from a monomer protective layer can be suppressed, the dry film resist roll which provides a resist pattern with high resolution adhesiveness is provided. Moreover, according to this invention, the method of forming a resist pattern on a board | substrate using this dry film resist roll, and the method of manufacturing various members using this dry film resist roll are also provided.

  Hereinafter, the present invention will be specifically described.

<Dry film resist roll>
One embodiment of the present invention is a dry film resist roll in which a photosensitive resin laminate is wound around a winding core, and the photosensitive resin laminate includes a support (A), a photosensitive resin layer (B), and It has a protective layer (C) so as to be positioned in this order, and the photosensitive resin layer (B) is (a) a thermoplastic polymer containing a carboxyl group (hereinafter referred to as (a) a thermoplastic polymer). 20 to 90% by mass, (b) 5 to 75% by mass of an addition polymerizable monomer (hereinafter also referred to as (b) 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, the free volume of the protective layer (C) is less than 0.2 nm ³ , and the internal pressure applied to the winding core is 0.1 MPa or more. A dry film resist roll is provided.

  Moreover, another aspect of the present invention is a dry film resist roll in which a photosensitive resin laminate is wound around a core, and the photosensitive resin laminate comprises a support (A), a photosensitive resin layer ( B) and a protective layer (C) so as to be positioned in this order, the photosensitive resin layer (B) is (a) 20 to 90% by mass of a thermoplastic polymer containing a carboxyl group, (b The protective layer (C) contains 5 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. ) Is a polypropylene film, and provides a dry film resist roll having an internal pressure applied to the winding core of 0.1 MPa or more.

[Support (A)]
The support (A) 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 these films, those stretched as necessary can be used. The haze of the support (A) is preferably 5 or less. The thinner the support (A) is, the more advantageous in terms of image formability and economy, but a film having a thickness of 10 to 30 μm is preferably used because the strength needs to be maintained.

  The surface roughness (Ra) (namely, centerline average roughness) of the support (A) of the present invention is the surface opposite to the photosensitive resin layer (B) lamination side (namely, photosensitive in a typical embodiment). The surface exposed as the surface of the resin laminate is preferably 0.001 to 0.06 μm. When the surface roughness (Ra) is 0.001 μm or more, the film surface is hardly scratched during film formation, and when it is 0.06 μm or less, the resist pattern is less likely to be jagged or chipped. The surface roughness (Ra) is more preferably 0.015 to 0.045 μm. When the surface roughness (Ra) is 0.015 μm or more, it is advantageous from the viewpoint that the adhesion between films is suppressed and the workability is good, and when it is 0.045 μm or less, the image formability is high. This is also advantageous in that it is difficult to deteriorate.

  The surface roughness (Ra) (namely, centerline average roughness) here is measured with a surface roughness measuring machine (for example, URFCOM-130A manufactured by Tokyo Seimitsu). The surface roughness (Ra) is defined by JIS B0601, and has a cutoff of 0.25 mm and an evaluation length of 1.25 mm.

[Photosensitive resin layer (B)]
The photosensitive resin layer (B) comprises (a) 20 to 90% by mass of a thermoplastic polymer, (b) 5 to 75% by mass of an addition polymerizable monomer, and (c) 0.01 to 30% by mass of a photopolymerization initiator. For example, the photosensitive resin composition prepared so as to include the components (a), (b), and (c) above can be formed by applying the composition on an arbitrary surface.

(A) Thermoplastic polymer The (a) thermoplastic polymer used in the present invention is a polymer having a carboxyl group and typically having an α, β-unsaturated carboxyl group-containing monomer as a polymerization component. . (A) The carboxyl group in the thermoplastic polymer is necessary for the photosensitive resin layer (B) to have developability and releasability with respect to the developer and release solution made of an alkaline aqueous solution.

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

(A) The weight average molecular weight of the thermoplastic polymer is preferably 5,000 to 500,000. The weight average molecular weight is preferably 5,000 or more from the viewpoint of maintaining a uniform thickness of the photosensitive resin laminate (that is, a dry film resist) and obtaining resistance to the developer, and maintain developability. In view of the above, it is preferably 500,000 or less. More preferably, the weight average molecular weight is 20,000 to 300,000. The weight average molecular weight in the present specification means a weight average molecular weight measured by gel permeation chromatography (GPC) using a calibration curve of 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

  (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 preferable that they are two or more types of copolymers, or a copolymer of one or more of the first monomers and one or more of the second monomers.

  The first monomer is a carboxylic acid or carboxylic anhydride having one polymerizable unsaturated group in the molecule. Examples of the first monomer 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 good developability. Here, (meth) acryl indicates acryl or methacryl. The same applies hereinafter.

  The second monomer is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, and iso-butyl. (Meth) acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate And esters of vinyl alcohol such as 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 good 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 content of the thermoplastic polymer (a) in the photosensitive resin layer (B) is in the range of 20 to 90% by mass, and preferably in the range of 25 to 70% by 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 typically a terminal ethylenically unsaturated group. As the (b) addition polymerizable monomer, those having a molecular weight of 450 or less are preferable from the viewpoint of obtaining a high-resolution adhesion pattern. The (b) addition polymerizable monomer is more preferably a low molecular weight monomer having a molecular weight of 350 or less, which is also preferable from the viewpoint of good positive pattern removal.

  Furthermore, from the viewpoint of high resolution and edge fuse resistance, the photosensitive resin composition (B) is represented by the following general formula (I) as (b) addition polymerizable monomer:

(In the formula, 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 3-20.)
Or 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 at least one photopolymerizable unsaturated compound represented by the formula:

In the compound represented by the general formula (I), n ₁ , n ₂ and n ₃ are each independently 3 or more and 20 or less. n ₁ , n ₂ and n ₃ are 3 or more in terms of good tenting properties and 20 or less in terms of good sensitivity and resolution. n ₁ and n ₃ are each independently more preferably 3 or more and 10 or less, and n ₂ is more preferably 5 or more and 15 or less.

In the compound represented by the general formula (II), n ₄ and n ₅ are each independently from the viewpoints of flexibility and tenting properties of a cured resist film obtained by curing the photosensitive resin layer (B). 1 or more and n ₄ + n ₅ is 2 or more. Further, from the viewpoint of obtaining a good effect on resolution, n ₄ and n ₅ are each independently 29 or less and n ₄ + n ₅ is 30 or less, n ₆ and n ₇ are each independently 29 or less and n ₆ + N ₇ is 30 or less.

The value of n ₄ + n ₅ + n ₆ + n ₇ is preferably 2 or more, and more preferably 40 or less. The above value is preferably 2 or more from the viewpoint of flexibility and tenting properties of the cured resist film obtained by curing the photosensitive resin layer (B), and the above value is preferably 40 or less from the viewpoint of obtaining a good effect on resolution. .

  Specific examples of the unsaturated compound represented by the above general formula (II) include polyethylene glycol dimethacrylate (for example, NK manufactured by Shin-Nakamura Chemical Co., Ltd.) having an average of 2 moles of ethylene oxide added to both ends of bisphenol A. Ester BPE-200) and polyethylene glycol dimethacrylate (for example, 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 bisphenol A, respectively. Polyalkylene glycol dimethacrylate with 6 moles of ethylene oxide and 2 moles of propylene oxide added on average, polyamine glycol with an average of 15 moles of ethylene oxide and 2 moles of propylene oxide added on both ends of bisphenol A, respectively. Dimethacrylate sharp glycol, and the like.

  (B) The proportion of the photopolymerizable unsaturated compound represented by the general formula (I) in the addition polymerizable monomer is 3% in terms of good sensitivity, resolution, adhesion and tenting properties. % Or more is preferable, and 70 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 in terms of good 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.

  As the addition polymerizable monomer (b), in addition to the compounds represented by the general formulas (I) and (II), known compounds having at least one polymerizable ethylenically unsaturated bond 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 group (meth) acrylate containing urethane group such as urethanized product of hexamethylene diisocyanate and nonapropylene glycol monomethacrylate, and polyfunctional (meth) acrylate of isocyanuric acid ester compound Is mentioned. These may be used alone or in combination of two or more.

  The content of the (b) addition polymerizable monomer in the photosensitive resin layer (B) is in the range of 5 to 75% by mass, and preferably in the range of 15 to 70% by mass. The above content is 5% by mass or more from the viewpoint of suppressing the curing failure of the photosensitive resin layer (B) and the delay of the development time, and 75 from the viewpoint of suppressing the cold flow and the delay in peeling of the cured resist. It is below mass%.

(C) Photopolymerization initiator (c) As the photopolymerization initiator, those usually used as photopolymerization initiators for photosensitive resins can be used as appropriate. In particular, hexaarylbisimidazole (hereinafter referred to as triarylimidazolyl dimer). The body is also 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 the resolution and the strength of the cured resist film, and is preferably used. These may be used alone or in combination of two or more.

  (C) The use of an acridine compound or a pyrazoline compound as a photopolymerization initiator is preferable from the viewpoint of obtaining good 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 and the like. Of these, 9-phenylacridine is preferable.

  Examples of the pyrazoline compound include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 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 photopolymerization initiators other than the above include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1 Quinones such as -chloroanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone; Aromatic ketones such as benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], and 4,4′-bis (diethylamino) benzophenone, benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethyl Benzoin ethers such as benzoin, benzyl dimethyl ketal, benzyl diethyl ketal, combinations of thioxanthones and alkylaminobenzoic acid, and 1-phenyl-1,2-propanedione-2-O-benzoin oxime and 1-phenyl- Examples include oxime esters such as 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 dimethylamino. A combination with ethyl benzoate is mentioned. N-aryl amino acids may also be used. 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 layer (B) is the range of 0.01-30 mass%, Preferably, it is the range of 0.05-10 mass%. The content is 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity at the time of photopolymerization by exposure, and also to the bottom surface of the photosensitive resin layer (B) at the time of photopolymerization (that is, a portion far from the light source). It is 30% by mass or less from the viewpoint of sufficiently transmitting light and obtaining good resolution and adhesion.

Other components Various additives can be contained in the photosensitive resin layer (B) as other components of the components (a) to (c). Specifically, for example, coloring substances such as 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 contain the color former in the photosensitive resin layer (B) so that a visible image can be given by exposure. Examples of color developing dyes that can be used as such color formers include leuco dyes or combinations of fluoran 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 former in the photosensitive resin layer (B) 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, the point that the contrast between the exposed part and the unexposed part is good, and the point that the storage stability is good. To 10% by mass or less is preferable.

  Furthermore, in order to improve the thermal stability and storage stability of the photosensitive resin layer (B), the photosensitive resin layer (B) is selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles. It is preferable to contain one or more 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 total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles in the photosensitive resin layer (B) is preferably 0.01 to 3% by mass, more preferably 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 layer (B), and 3% by mass or less from the viewpoint of maintaining good exposure sensitivity. More preferred.

  You may make the photosensitive resin layer (B) contain a plasticizer as needed. 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, polyoxyethylene monomethyl ether, Glycol esters such as oxypropylene monoethyl ether and polyoxyethylene polyoxypropylene monoethyl ether, phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, citric acid Triethyl acid, triethyl acetyl citrate, tri-n-propyl acetyl citrate, and tri-n-butyl acetyl citrate And the like.

  The content of the plasticizer in the photosensitive resin layer (B) is preferably 5 to 50% by mass, and more preferably 5 to 30% by 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.

  The film thickness of the photosensitive resin layer (B) is preferably 5 to 100 μm, more preferably 7 to 60 μm. The thinner the film thickness, the better the resolution, and the thicker the film thickness, the better the film strength. Therefore, the film thickness can be appropriately selected according to the application.

(Photosensitive resin composition preparation)
The photosensitive resin layer (B) can be formed by applying a photosensitive resin composition prepared so as to include the components described above. In forming the photosensitive resin layer (B), a photosensitive resin composition preparation liquid obtained by adding a solvent to the photosensitive resin composition can be employed in various applications. 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 added to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid is 500 to 4000 mPa · sec at 25 ° C. when measured with a rotational viscometer.

[Protective layer (C)]
The protective layer (C) is formed for the purpose of protecting the photosensitive resin layer (B). An important characteristic of the protective layer used in the dry film resist 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. As a material of the protective layer (C), a polypropylene film is preferable.

  The thickness of the protective layer (C) is preferably 10 to 100 μm, and more preferably 15 to 70 μm. When the film thickness is 10 μm or more, it is advantageous in that air void generation is suppressed, and when it is 100 μm or less, it is advantageous in that it is not bulky when formed into a roll.

In one embodiment of the present invention, the protective layer (C) has a free volume of less than 0.2 nm ³ . According to this aspect, it can suppress that the low molecular weight monomer originating in the photosensitive resin layer (B) bleeds out from a protective layer (C) especially. The free volume is more preferably 0.10 nm ³ or less. Here, the free volume is a void in a solid that instantaneously generates and disappears with the molecular motion of the polymer. It is known that the free volume of a polymer has a strong correlation with the glass transition phenomenon, relaxation phenomenon, rheological properties, mechanical properties, thermal expansion coefficient, and the like.

  The free volume of the polymer film can be measured using the positron annihilation lifetime method. Specifically, measure the time from when a positron is incident on the sample until it annihilates, and observe nondestructively the information about the size of vacancies and free volume, number concentration, etc. from the annihilation lifetime. Thus, the free volume can be obtained. In addition, the free volume described in this specification is a value at room temperature.

  The positron annihilation lifetime method is described in, for example, Toray Research Center THE TRC NEWS No. 80 (Jul. 2002) p20-22, Journal of Polymer Science. Part B. Polymer Physics vol. 41 no. 23 p3089-3093, which can be referred to.

The oxygen permeability in terms of the room temperature and 25 μm thickness of the protective layer (C) is preferably less than 7,000 cc / m ² · 24 hr · atm. In this case, it is effective for suppressing bleed out of low molecular weight monomers. The oxygen permeability is more preferably less than 4,500 cc / m ² · 24 hr · atm.

  In addition, the measurement conditions of the oxygen permeability of the polymer film in this invention are 25 degreeC and 0% RH, and follow ASTM D-1434.

In another embodiment of the present invention, a polypropylene film is used as the protective layer (C). According to this aspect, the effect of suppressing bleed out of low molecular weight monomers derived from the photosensitive resin layer (B) can be obtained. A preferred property of this polypropylene film is that the free volume is usually less than 0.2 nm ³ .

  The dry film resist roll of the present invention can be produced by sequentially laminating the support (A), the photosensitive resin layer (B), and the protective layer (C) by a conventionally known method. For example, the photosensitive resin composition for forming the photosensitive resin layer (B) is mixed with a solvent for dissolving the photosensitive resin composition to prepare a uniform solution as a photosensitive resin composition preparation solution. This is first coated on the support (A) using a bar coater or roll coater and dried, and a photosensitive resin layer (B) made of a photosensitive resin composition is laminated on the support (A). Next, a dry film resist can be produced by laminating the protective layer (C) on the photosensitive resin layer (B).

The dry film resist obtained as described above, after coating and drying the photosensitive resin layer (B), is once wound up to a length of 500 m or more on the winding core, and then the width according to the intended use. And slit to the winding length. In the present invention, the internal pressure applied to the core portion of the dry film resist roll obtained by the winding after the coating and the winding after the slit is 0.1 MPa or more from the viewpoint of suppressing the winding deviation of the resist roll. . Usually, the dry film resist roll wound up to have an internal pressure of 0.1 MPa or more may cause temporary attachment failure due to bleeding because the support and the protective layer are in close contact with each other. Since the free volume of the protective layer (C) is less than 0.2 nm ³ or the protective layer (C) is a polypropylene film, bleeding can be suppressed. The internal pressure applied to the core part of the dry film resist roll is preferably 0.1 to 5 MPa. The internal pressure is preferably 5 MPa or less from the viewpoint of storage stability of the film shape. Further, if the internal pressure is in the range of 0.1 to 5 MPa, any temporary pressure does not cause a defective tack due to the effect of the protective layer (C) used in the present invention as described above. The internal pressure is more preferably 0.3 to 2 MPa. The internal pressure is more preferably 0.3 MPa or more from the viewpoint of suppressing movement of the resist roll and winding deviation at the time of movement, and further preferably 2 MPa or less from the viewpoint of suppressing edge fuse. The internal pressure is particularly preferably 0.3 to 1 MPa. From the viewpoint of suppressing edge fuse during distribution, it is particularly preferably 1 MPa or less.

  In this specification, the internal pressure applied to the winding core is a value measured using a pressure measurement film (for example, a prescale which is a pressure measurement film manufactured by Fuji Film Business Supply Co., Ltd.). Typically, when the dry film resist is wound on a roll, a prescale is placed on the core, left to stand for 5 minutes or more, and then wound to take out the prescale. Ten pre-scaled densitometers (for example, trade name: FPD-305E) are used to measure 10 points at random and determine an average value.

  The dry film resist roll of the present invention typically comprises a support (A), a photosensitive resin layer (B), and a protective layer (C). In addition to these, any layer (for example, a cushion layer, An oxygen barrier layer or the like.

<Resist pattern formation method>
Another aspect of the present invention includes a laminating step of forming a photosensitive resin layer on a substrate using the dry film resist roll of the present invention described above, an exposing step of exposing the photosensitive resin layer, and a post-exposure step Provided is a resist pattern forming method including a developing step of developing a photosensitive resin layer to form a resist pattern. An example of a specific method is shown below.

[Lamination process]
In this step, for example, a laminator is used, and a photosensitive resin layer is formed on the substrate using the dry film resist roll of the present invention. More specifically, after removing the protective layer (C) while paying out the dry film resist roll of the present invention, the photosensitive resin layer (B) is laminated on the substrate, and the substrate is adhered by heating and pressing. A photosensitive resin layer can be formed thereon. In order to sufficiently match the unevenness of the substrate and coat the substrate with the photosensitive resin layer, it is effective to perform the lamination under reduced pressure. 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.

[Exposure process]
In this step, the photosensitive resin layer is exposed using an exposure machine. If necessary, the support (A) 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, and may be measured using a light meter.

  In the exposure step, a maskless exposure method may be used. In maskless exposure, 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 is used. The drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the illuminance of the exposure light source and the moving speed of the substrate.

[Development process]
In this step, the exposed photosensitive resin layer is developed using a developing device. After the exposure, when the support (A) is on the photosensitive resin layer, the support (A) is removed. Subsequently, the unexposed portion is developed and removed using a developer composed of an alkaline aqueous solution to obtain a resist image. As the alkaline aqueous solution, an aqueous solution of Na ₂ CO ₃ , K ₂ CO ₃ or the like is preferable. These are selected in accordance with the characteristics of the photosensitive resin layer, but 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, 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 of a hot air, infrared ray, far infrared ray, or the like can be used.
A resist pattern can be formed by the above method.

<Conductor pattern manufacturing method>
Another aspect of the present invention is a laminating step in which a photosensitive resin layer is formed on a substrate that is a metal plate or a metal film insulating plate using the dry film resist roll of the present invention described above. Production of a conductor pattern, including an exposure step of exposing, a developing step of developing the photosensitive resin layer after the exposure to form a resist pattern, and a conductor pattern forming step of etching or plating the substrate on which the resist pattern is formed Provide a method.

  The method for producing a conductor pattern of the present invention further includes the following steps after a resist pattern is formed by the above-described resist pattern forming method using a metal plate or a metal film insulating plate as a substrate.

[Conductor pattern forming process]
In this step, the substrate on which the resist pattern is formed is etched or plated by the method described above. That is, a conductor pattern is formed on the surface (for example, copper surface) of the substrate exposed by development using a conventionally known etching method or plating method.

<Method for manufacturing printed wiring board>
Another aspect of the present invention is a laminating step of forming a photosensitive resin layer on a substrate that is a copper-clad laminate or a flexible substrate using the dry film resist roll of the present invention described above, and exposing the photosensitive resin layer. An exposure step for developing, a development step for developing the exposed photosensitive resin layer to form a resist pattern, and a wiring formation step for etching or plating the substrate on which the resist pattern is formed and then peeling the resist pattern. A method of manufacturing a printed wiring board is provided.

  The method for producing a printed wiring board of the present invention further includes the following steps after a copper-clad laminate or a flexible substrate is used as a substrate and a resist pattern is formed by the above-described resist pattern forming method.

[Wiring formation process]
In this step, a conductor pattern is formed on the surface (for example, copper surface) of the substrate exposed by development in the formation of the resist pattern by the above-described method using a conventionally known etching method or plating method, and then developed. The resist pattern is peeled from the substrate with an aqueous solution having alkalinity stronger than the liquid to obtain a desired printed wiring board. There is no particular limitation on the alkaline aqueous solution for stripping (hereinafter also referred to as “stripping solution”), but an aqueous solution of NaOH or KOH having a concentration of 2 to 5 mass% is generally used. It is also 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 is the range of 40-70 degreeC.

<Lead frame manufacturing method>
Another aspect of the present invention includes a laminating step of forming a photosensitive resin layer on a substrate that is a metal plate using the dry film resist roll of the present invention described above, an exposure step of exposing the photosensitive resin layer, A lead frame manufacturing method comprising: a developing step of developing a photosensitive resin layer after exposure to form a resist pattern; a lead frame forming step of etching the substrate on which the resist pattern is formed and then peeling the resist pattern; provide.

  The lead frame manufacturing method of the present invention includes the following steps after forming a resist pattern by the above-described resist pattern forming method using a metal plate such as copper, a copper alloy, and an iron-based alloy as a substrate.

[Lead frame forming process]
In this step, the surface of the substrate exposed by development in the formation of the resist pattern by the method described above is etched by a conventionally known method to form a conductor pattern, and then the resist pattern is formed on the printed wiring board described above. Peeling is performed in the same manner as the manufacturing method to obtain a desired lead frame.

<Manufacturing method of substrate having concave / convex pattern>
Another aspect of the present invention is a laminate process for forming a photosensitive resin layer on a substrate using the dry film resist roll of the present invention described above, an exposure process for exposing the photosensitive resin layer, and a photosensitivity after the exposure. A substrate having a concavo-convex pattern, comprising: a development step of developing a resist resin layer to form a resist pattern; and a concavo-convex pattern forming step of processing the substrate on which the resist pattern is formed by a sandblasting method and then peeling the resist pattern A manufacturing method is provided.

  The manufacturing method of the base material which has an uneven | corrugated pattern of this invention further includes an uneven | corrugated pattern formation process, after forming a resist pattern by the above-mentioned resist pattern formation method. The resist pattern can be used as a protective mask member when processing the substrate by a sandblasting method.

Examples of the substrate include glass, silicon wafer, amorphous silicon, polycrystalline silicon, ceramic, sapphire, and metal material. A resist pattern is formed on the substrate such as glass by the same method as the resist pattern forming method described above. After that, in the concavo-convex pattern forming process, the blasting material is sprayed onto the substrate from the formed resist pattern, and sandblasting is performed by a sandblasting method for cutting to the desired depth, and then the substrate by an alkali stripping solution of the resist pattern portion remaining on the substrate A substrate having a fine concavo-convex pattern on the substrate can be produced through peeling and removal from the substrate. As the blasting material used for the sandblasting, known materials are used. For example, fine particles having a diameter of about 2 to 100 μm such as SiC, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO, glass, and stainless steel are used.

<Semiconductor package manufacturing method>
Another aspect of the present invention is a laminating process in which a photosensitive resin layer is formed on a substrate, which is a wafer on which circuit formation as LSI has been completed, using the dry film resist roll of the present invention described above, and the photosensitive resin layer An exposure step of exposing the substrate, a development step of developing the exposed photosensitive resin layer to form a resist pattern, a plating step of plating the substrate on which the resist pattern is formed, and then peeling off the resist pattern. A method for manufacturing a semiconductor package is provided.

  The semiconductor package manufacturing method of the present invention further includes the following steps after a resist pattern is formed by the above-described resist pattern forming method using a wafer in which circuit formation as an LSI has been completed as a substrate.

[Package formation process]
In this step, a conductor pattern is formed by applying columnar plating such as copper or solder to the opening exposed by development in the formation of the resist pattern by the method as described above. Next, the resist pattern is peeled by the same method as the above-described printed wiring board manufacturing method. Further, preferably, the thin metal layer in the portion other than the columnar plating is removed by etching. Thereby, a desired semiconductor package can be obtained.

  Below, the preparation methods of the sample for evaluation of an Example and a comparative example, and the evaluation method and evaluation result about the obtained sample are shown.

1. Production of Evaluation Samples The dry film resist rolls in Examples 1 to 5 and Comparative Examples 1 and 2 were produced as follows.

<Production of dry film resist roll>
The compounds shown in Table 1 below are prepared, and the photosensitive resin composition having the composition ratio shown in Table 2 below (the value in the table is parts by mass) is mixed with methyl ethyl ketone (MEK) which is a solvent for dissolving them. The mixture was thoroughly stirred and mixed to obtain a photosensitive resin composition preparation solution having a uniform solution. A photosensitive resin layer (B) was formed on the surface of a polyethylene terephthalate film having a film thickness of 16 μm as the support (A) by uniformly applying the photosensitive resin composition preparation liquid using a bar coater and drying it. . The surface roughness (Ra) of the support was 0.03 μm on the surface on which the photosensitive resin layer (B) was not laminated. The film thickness of the photosensitive resin layer (B) was 25 μm.

  Next, on the surface of the photosensitive resin layer (B) on which the support (A) is not laminated, a polypropylene film is used as a protective layer (C) (protective film) in Examples 1 to 5 and Comparative Example 2. In Comparative Example 1, a polyethylene film was laminated to obtain a dry film resist.

  Subsequently, the obtained dry film resist was wound up to a length of 200 m at an internal pressure shown in Table 2 to obtain a dry film resist roll.

<Board surface preparation>
As a substrate to be used for measuring resolution and adhesion, a 0.4 mm thick copper clad laminate on which 35 μm rolled copper foil is laminated, and jet scrub polishing (manufactured by Nippon Carlit Co., Ltd.) at a spray pressure of 0.20 MPa. , Using Sac Random R (registered trademark) # 220.

<Laminate>
A hot roll laminator (ALA-700, manufactured by Asahi Kasei Co., Ltd.) is applied to a copper-clad laminate that has been surface-prepared and preheated to 60 ° C. And laminated at a roll temperature of 105 ° C. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.

<Exposure>
A chromium glass mask necessary for evaluating the photosensitive resin layer (B) is placed on a polyethylene terephthalate film as the support (A), and an ultra-high pressure mercury lamp (manufactured by Oak Manufacturing Co., Ltd., parallel light exposure apparatus HMW-801). Thus, the photosensitive resin layer (B) was exposed with an exposure amount at which the 21-step tablet made by Stöffer becomes 4 steps.

<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 (manufactured by Fuji Kiko Co., Ltd., a dry film developing machine). Unexposed portions were 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) Protective layer free volume Toray Research Center THE TRC NEWS No. 80 (Jul. 2002) p20-22, Journal of Polymer Science. Part B. Polymer Physics vol. 41 no. 23 Reference was made to the values described in p3089-3093.
(2) Sensitivity Evaluation A substrate for sensitivity and resolution evaluation that had passed for 15 minutes after lamination was exposed using a 27-step tablet manufactured by Asahi Kasei whose brightness was changed from transparent to black in 27 steps. 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.

(3) Resolution Evaluation The substrate for resolution evaluation that had passed 15 minutes after the 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 width in which a cured resist line was normally formed was defined as a resolution value, and the resolution was ranked as follows:
A: The resolution value is 7.5 μm or less;
○: Resolution value is over 7.5 μm and 8.5 μm or less;
X: The resolution value is more than 8.5 μm.

(4) Adhesion Evaluation The substrate for sensitivity and resolution evaluation that had passed 15 minutes after lamination was exposed through a line pattern mask having a ratio of the width of the exposed area to the unexposed area of 1: 1. 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 adhesion value:
A: Adhesion value is 13 μm or less;
○: Adhesion value of more than 13 μm and 14 μm or less;
X: Adhesiveness value exceeds 14 μm.

(5) Tackiness evaluation A dry film resist roll is fed out, and a protective resin is peeled off. Then, a photosensitive resin layer (B) is placed on a copper-clad laminate that has been leveled and preheated to 50 ° C., and a laminator with a tacking block ( Asahi Engineering Co., Ltd., ACL-8100) was used for crimping at a tacking temperature of 50 ° C., a tacking time of 2 seconds, and a tacking pressure of 0.4 MPa. The ranking was then as follows:
○: The support is completely separated from the tacking block and is tacked without any problem;
Δ: Temporary attached, but support attached to the side of the temporary attachment block;
X: The support is stuck to the entire surface of the temporary block, and the temporary attachment is peeled off.

(6) Evaluation of edge fuse property The wound dry film resist roll was placed in a thermostatic layer at 25 ° C., and the end face was observed after 10 days and evaluated as follows.
○: No abnormality is observed on the end face.
X: The resin layer oozes out to the end surface.

(7) Winding evaluation The wound dry film resist roll was stored with its end face up and down, observed for winding after one day, and further dropped freely from a drop height of 5 cm, and observed for winding, as follows. Evaluated.
A: The dry film resist is not wound off from the winding core after free fall.
○: There is no winding slip after one day of storage, but the dry film resist is slipping from the core after free fall.
X: The dry film resist is wound from the winding core one day after storage.

(8) Roll internal pressure The internal pressure of the dry film resist roll was measured using a prescale which is a pressure measurement film manufactured by Fuji Film Business Supply Co., Ltd. When winding up the resist roll, a prescale was placed on the winding core and allowed to stand for 5 minutes or more, and then wound up to take out the prescale. Ten prescaled densitometers (trade name: FPD-305E) were used to measure 10 points at random, and the average value was determined. For the measurement, an ultra-low pressure prescale was used.

  The evaluation results of Examples 1 to 5 and Comparative Examples 1 to 2 are shown in Table 2 below.

  The present invention is the manufacture of printed wiring boards, IC chip mounting lead frames, metal foil precision processing such as metal mask manufacturing, BGA, CSP and other package manufacturing, COF, TAB and other tape substrate manufacturing, and semiconductor bump manufacturing. In addition, the present invention can be used in a method for manufacturing partition walls of flat panel displays such as ITO electrodes, address electrodes, and electromagnetic wave shields.

Claims (7)

A method for producing a conductor pattern using a dry film resist roll in which a photosensitive resin laminate is wound around a winding core,
The photosensitive resin laminate has a support (A), a photosensitive resin layer (B), and a protective layer (C) so as to be positioned in this order,
The photosensitive resin layer (B) is (a) 20 to 90% by mass of a thermoplastic polymer containing a carboxyl group, and (b) addition polymerizable having at least one polymerizable ethylenically unsaturated bond in the molecule. Including 5 to 75% by weight of monomer, and (c) 0.01 to 30% by weight of a photopolymerization initiator,
The protective layer (C) is:
(I) is a polypropylene film, and
(Ii) The free volume is less than 0.2 nm ³
Satisfy at least one of
A laminating step of forming a photosensitive resin layer on a substrate that is a metal plate or a metal film insulating plate using a dry film resist roll having an internal pressure applied to the winding core of 0.1 MPa or more ,
An exposure step of exposing the photosensitive resin layer;
A method comprising : a developing step of developing the exposed photosensitive resin layer to form a resist pattern; and a conductor pattern forming step of etching or plating the substrate on which the resist pattern is formed. A method for producing a printed wiring board using a dry film resist roll in which a photosensitive resin laminate is wound around a winding core,
The photosensitive resin laminate has a support (A), a photosensitive resin layer (B), and a protective layer (C) so as to be positioned in this order,
The photosensitive resin layer (B) is (a) 20 to 90% by mass of a thermoplastic polymer containing a carboxyl group, and (b) addition polymerizable having at least one polymerizable ethylenically unsaturated bond in the molecule. Including 5 to 75% by weight of monomer, and (c) 0.01 to 30% by weight of a photopolymerization initiator,
The protective layer (C) is:
(I) is a polypropylene film, and
(Ii) The free volume is less than 0.2 nm ³
Satisfy at least one of
A laminating step of forming a photosensitive resin layer on a substrate which is a copper-clad laminate or a flexible substrate using a dry film resist roll having an internal pressure applied to the winding core of 0.1 MPa or more ,
An exposure step of exposing the photosensitive resin layer;
A developing step of forming a resist pattern by developing the said exposure photosensitive resin layer after the light, and the resist pattern substrate formed by etching or plating, and then including a wiring forming step of removing the resist pattern, the method. A method of producing a lead frame using a dry film resist roll in which a photosensitive resin laminate is wound around a winding core,
The photosensitive resin laminate has a support (A), a photosensitive resin layer (B), and a protective layer (C) so as to be positioned in this order,
The photosensitive resin layer (B) is (a) 20 to 90% by mass of a thermoplastic polymer containing a carboxyl group, and (b) addition polymerizable having at least one polymerizable ethylenically unsaturated bond in the molecule. Including 5 to 75% by weight of monomer, and (c) 0.01 to 30% by weight of a photopolymerization initiator,
The protective layer (C) is:
(I) is a polypropylene film, and
(Ii) The free volume is less than 0.2 nm ³
Satisfy at least one of
A laminating step of forming a photosensitive resin layer on a substrate that is a metal plate using a dry film resist roll having an internal pressure applied to the winding core of 0.1 MPa or more ,
An exposure step of exposing the photosensitive resin layer;
A development step of developing the photosensitive resin layer after the exposure to form a resist pattern;
The substrate to which the resist pattern is formed by etching, and then includes a lead frame forming step of removing the resist pattern, the method. A method for producing a substrate having a concavo-convex pattern using a dry film resist roll in which a photosensitive resin laminate is wound around a winding core,
The photosensitive resin laminate has a support (A), a photosensitive resin layer (B), and a protective layer (C) so as to be positioned in this order,
The photosensitive resin layer (B) is (a) 20 to 90% by mass of a thermoplastic polymer containing a carboxyl group, and (b) addition polymerizable having at least one polymerizable ethylenically unsaturated bond in the molecule. Including 5 to 75% by weight of monomer, and (c) 0.01 to 30% by weight of a photopolymerization initiator,
The protective layer (C) is:
(I) is a polypropylene film, and
(Ii) The free volume is less than 0.2 nm ³
Satisfy at least one of
A laminating step of forming a photosensitive resin layer on a substrate using a dry film resist roll , wherein the internal pressure applied to the winding core is 0.1 MPa or more ;
An exposure step of exposing the photosensitive resin layer;
A development step of developing the photosensitive resin layer after the exposure to form a resist pattern;
An uneven pattern forming step of processing the substrate on which the resist pattern is formed by a sandblasting method and then peeling the resist pattern;
Including, METHODS. A method of manufacturing a semiconductor package using a dry film resist roll in which a photosensitive resin laminate is wound around a winding core,
The photosensitive resin laminate has a support (A), a photosensitive resin layer (B), and a protective layer (C) so as to be positioned in this order,
The photosensitive resin layer (B) is (a) 20 to 90% by mass of a thermoplastic polymer containing a carboxyl group, and (b) addition polymerizable having at least one polymerizable ethylenically unsaturated bond in the molecule. Including 5 to 75% by weight of monomer, and (c) 0.01 to 30% by weight of a photopolymerization initiator,
The protective layer (C) is:
(I) is a polypropylene film, and
(Ii) The free volume is less than 0.2 nm ³
Satisfy at least one of
A laminating step of forming a photosensitive resin layer on a substrate, which is a wafer on which circuit formation as LSI has been completed, using a dry film resist roll having an internal pressure applied to the winding core of 0.1 MPa or more ,
An exposure step of exposing the photosensitive resin layer;
A development step of developing the photosensitive resin layer after the exposure to form a resist pattern;
Plated substrate the resist pattern is formed, then including the package forming step of removing the resist pattern, the method. The surface roughness (Ra) of the surface opposite to the photosensitive resin layer (B) lamination side of the support (A) is 0.001 to 0.06 μm, 6. The method according to item . As the addition polymerizable monomer (b) having at least one polymerizable ethylenically unsaturated bond in the molecule, the following general formula (I):

(In the formula, 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 3-20.)
Or 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 method of any one of Claims 1-6 containing the photopolymerizable unsaturated compound represented by these.