JP2012226254A - Dry film resist roll - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dry film resist roll suppressing bleed-out of a monomer in a photosensitive resin through a protective layer, to provide a method for forming a resist pattern on a substrate by using the dry film resist roll, and to provide use application of the resist pattern.SOLUTION: The dry film resist roll comprises a photosensitive resin laminate wound on a roll core, in which the photosensitive resin laminate comprises a support (A), a photosensitive resin layer (B) and a protective layer (C), laminated in this order. The photosensitive resin layer (B) includes (a) 20 to 90 mass% of a thermosetting polymer containing a carboxyl group, (b) 5 to 75 mass% of an addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule, and (c) 0.01 to 30 mass% of a photopolymerization initiator. The protective layer (C) comprises a propylene-based copolymer film.

Description

  The present invention uses a dry film resist roll in which a photosensitive resin laminate having a photosensitive resin layer developable with an alkaline aqueous solution, a support, and a protective layer is wound around a winding core, and the dry film resist roll. The present invention relates to a method for forming a resist pattern on a substrate and 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 (negative). After forming the resist pattern on the substrate and performing etching or plating treatment to form the conductor pattern by solubilizing the exposed area and removing it with a developer (in the case of a positive mold) A method of forming a conductor pattern on a substrate by peeling and removing the resist pattern from the 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.

  An example of 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 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 through hole (through hole) of the substrate and the via hole for interlayer connection are covered with a cured resist film so that the metal in the hole is not etched. This construction method is called a tenting method. For the etching step, for example, a solution of cupric chloride, ferric chloride, or copper ammonia complex is used. Finally, the resist pattern is peeled from the substrate with an aqueous alkali solution such as sodium hydroxide. A substrate having a conductor pattern, that is, a printed wiring board is manufactured through the above-described steps.

  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 use of low density polyethylene for the protective layer.

JP 2001-290278 A JP 2003-342307 A

  With the recent miniaturization of wiring intervals in printed wiring boards, the demand for high resolution is increasing for dry film resists. In order to impart high resolution, a photopolymerizable monomer having a low molecular weight is often used in the photosensitive resin layer. 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. Problems that soil the roll may occur. Also, dry film resists are often manufactured as roll products. In this case, since the protective layer and the support are in contact with each other, the monomer that has passed through the protective layer is transferred to the surface of the support, and the surface of the support becomes sticky, making it difficult for the support to be peeled off from the laminate temporary block. There is a problem of causing defects.

  The present invention provides a dry film resist roll in which a protective layer is excellent in flexibility and a bleed out of a monomer in a photosensitive resin layer is suppressed, and a resist pattern is formed on a substrate using the dry film resist roll. It is an object of the present invention to provide a method of forming and a use of the resist pattern.

  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,
A dry film resist roll, wherein the protective layer (C) is a propylene-based copolymer film.
[2] The dry film resist roll according to the above [1], wherein the propylene-based copolymer is a copolymer of 1) propylene and 2) ethylene and / or a C4 to C18 α-olefin.
[3] The dry film resist roll according to [1] or [2], wherein the propylene-based copolymer is a propylene-ethylene copolymer.
[4] In any one of the above [1] to [3], the compound (b) contains a compound having a molecular weight of 600 or less as an addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule. The dry film resist roll described.
[5] 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 , A is C ₂ H ₄ , B is C ₃ H ₆ , and n ₁ and n ₃ are each independently 1 to 29 N ₁ + n ₃ is an integer of 2-30, n ₂ and n ₄ are each independently an integer of 0-29, and n ₂ + n ₄ 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]-[4] containing the photopolymerizable unsaturated compound represented by these.
[6] 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 [5],
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.
[7] 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 [5],
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.

  According to the present invention, since the protective layer is excellent in flexibility and the bleeding out of the monomer in the photosensitive resin layer from the protective layer can be suppressed, a dry film resist that provides a resist pattern with high resolution and high adhesion A role is provided. The present invention also provides a method for forming a high-definition resist pattern on a substrate using the dry film resist roll, and a method for producing various high-definition members using the dry film resist roll. .

2 is a photograph showing a bleed-out property evaluation result in Example 1. FIG. 6 is a photograph showing a bleed-out property evaluation result in Comparative Example 1.

  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) thermoplastic polymer”. 20-90% by mass, (b) addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule (hereinafter referred to as “(b) addition polymerizable monomer”) There is provided a dry film resist roll comprising 5) to 75% by mass of (a) and (c) 0.01 to 30% by mass of a photopolymerization initiator, wherein the protective layer (C) is a propylene copolymer film.

[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 formation and economy, but it is preferable to maintain a predetermined strength. Specifically, a support having a thickness of 10 to 30 μm is preferably used.

  The surface roughness (Ra) (that is, the center line average roughness) of the support (A) used in the present invention is the surface opposite to the photosensitive resin layer (B) lamination side (that is, photosensitive in a typical embodiment). The surface exposed as the surface of the conductive 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 a value measured by a surface roughness measuring device (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. In addition, the acid equivalent described in this specification is a value measured by potentiometric titration with a 0.1 mol / L NaOH aqueous solution using a potentiometric titrator (for example, 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 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 measured under the following conditions using, for example, gel permeation chromatography manufactured by JASCO Corporation.
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. 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. (B) The addition polymerizable monomer preferably contains a compound having a molecular weight of 600 or less from the viewpoint of obtaining a pattern with high resolution and high adhesion. (B) The addition-polymerizable monomer preferably contains a low-molecular monomer having a molecular weight of 450 or less, more preferably a molecular weight of 350 or less, from the viewpoint of good positive pattern removal. On the other hand, the molecular weight of the compound contained as the (b) addition polymerizable monomer is preferably 200 or more, and more preferably 250 or more, from the viewpoint of suppression of monomer component volatilization during coating. The molecular weight is a value calculated from the chemical structural formula of the monomer.

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

Wherein R ₁ and R ₂ are each independently H or CH ₃ , A is C ₂ H ₄ , B is C ₃ H ₆ , and n ₁ and n ₃ are each independently 1 to 29 N ₁ + n ₃ is an integer of 2-30, n ₂ and n ₄ are each independently an integer of 0-29, and n ₂ + n ₄ 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 and n ₃ are each independently from the viewpoint of flexibility and tenting properties of a cured resist film obtained by curing the photosensitive resin layer (B). 1 or more and n ₁ + n ₃ is 2 or more. Further, from the viewpoint of obtaining a favorable effect on resolution, n ₁ and n ₃ are each independently 29 or less and n ₁ + n ₃ is 30 or less, n ₂ and n ₄ are each independently 29 or less and n ₂ + N ₄ is 30 or less. More preferably, n ₁ and n ₃ are each independently an integer of 1 to 14 and n ₁ + n ₃ is an integer of 2 to 15, n ₂ and n ₄ are each independently an integer of 0 to 9 and n ₂ + n ₄ is an integer of 0 to 10.

The value of n ₁ + n ₂ + n ₃ + n ₄ 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 general formula (I) 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), 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 average to both ends of bisphenol A Polyalkylene glycol dimethacrylate with 6 moles of ethylene oxide and 2 moles of propylene oxide added on average, and 15 moles of ethylene oxide and 2 moles of propylene oxide on the both ends of bisphenol A respectively. Dimethacrylate Ruki glycol, and the like.

  (B) The proportion of the photopolymerizable unsaturated compound represented by the general formula (I) in the addition polymerizable monomer is preferably 3% by mass or more, and preferably 10% by mass or more in terms of good sensitivity. More preferred is 15% by mass or more. Moreover, the said ratio is preferable 70 mass% or less from a viewpoint from which edge fuse is suppressed, 65 mass% or less is more preferable, and 55 mass% or less is further more preferable.

  As the addition polymerizable monomer (b), in addition to the compound represented by the general formula (I), a known compound 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 a reaction product of propylene oxide (for example, Nippon Shokubai Chemical Co., Ltd., trade name OE-A 200), 4-normal octylphenoxypentapropylene glycol acrylate, 1,6-hexanediol (meth) acrylate, 1,4-cyclohexanediol di Polyoxyalkylene glycol di (meth) such as (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate Acrylate, 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. , Also referred to as triarylimidazolyl dimer). 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 preferably 50% by mass or less from the viewpoint of suppressing insufficient curing and cold flow. 30 mass% or less is more preferable.

  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). One of the important characteristics 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 adhesive force with the photosensitive resin layer.

  The protective layer (C) in the present invention is a propylene-based copolymer film. Here, the propylene copolymer is a copolymer having a copolymerization ratio of propylene of 80 mol% or more and 99.9 mol% or less and a copolymerization ratio of components other than propylene of 0.1 mol% or more and 20 mol% or less. Point to. By using a propylene-based copolymer film as the protective layer (C), bleeding of the (b) addition polymerizable monomer can be suppressed. The dry film resist roll using the propylene copolymer film has, for example, a molecular weight of 600 or less, more specifically, a (b) addition polymerizable monomer having a molecular weight of 450 or less in the photosensitive resin layer (B) of 5% by mass or more. When included, the bleed suppressing effect is remarkable as compared with the case where, for example, a low density polyethylene (LDPE) film is used as the protective layer (C). When (b) addition polymerizable monomer having a molecular weight of 600 or less, more particularly 450 or less is contained in the photosensitive resin layer (B) in an amount of 10% by mass or more, the bleed suppression effect by the protective layer (C) is more remarkable. Demonstrated. When the (b) addition polymerizable monomer having a molecular weight of 350 or less is contained in the photosensitive resin layer (B), the bleed suppressing effect by the protective layer (C) is further remarkable.

  The propylene copolymerization ratio of the propylene-based copolymer film is preferably 94 mol% or more and 99 mol% or less. In this case, the copolymerization ratio of components other than propylene is 1 mol% or more and 6 mol%. The component other than propylene is not particularly limited as long as it is one or more types. As components other than propylene, ethylene, butene and the like are preferable from the viewpoint of lowering the melting point. From the viewpoint of film flexibility, the propylene-based copolymer is more preferably a copolymer of 1) propylene and 2) ethylene and / or a C4 to C18 α-olefin. Further, as the propylene-based copolymer, a propylene-ethylene copolymer is particularly preferable.

  The copolymerization mode of propylene and ethylene may be a random copolymer or a block copolymer. From the viewpoint of flexibility and transparency of the film, a random copolymer is preferable.

The copolymerization ratio of ethylene to 100 mol parts of propylene-ethylene copolymer is preferably 0.1 mol parts or more, more preferably 0.5 mol parts or more, and more preferably 1 mol part or more from the viewpoint of flexibility. Further preferred. Moreover, from a viewpoint of bleed-out suppression, 50 mol part or less is preferable, 20 mol part or less is more preferable, 10 mol part or less is further more preferable, and 6 mol part or less is further more preferable. The copolymerization ratio, a sample was dissolved at a concentration of 10 mass% at 130 to 140 ° C. in deuterated orthodichlorobenzene, by then After homogenization was left overnight to complete the coupling process at 130 ° C. ¹³ It can be determined by C-NMR measurement (for example, by ECS400 manufactured by JEOL).

The weight average molecular weight of the propylene-based copolymer is preferably 1,000 or more and 10,000,000 or less, and more preferably 10,000 or more and 1,000,000 or less. The weight average molecular weight is preferably 1,000 or more, and preferably 10,000,000 or less from the viewpoint of stickiness and bleed out. Further, the dispersity Mw / Mn is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, and further preferably 1 or more and 3.5 or less from the viewpoint of flexibility. The weight average molecular weight and dispersity are determined by the following method. The sample is added to orthodichlorobenzene in an amount so as to give a concentration of 1.0 mg / ml, and after standing treatment (145 ° C. × 1 h) using a dissolver (for example, a high-temperature dissolver manufactured by Senshu Chemical), rocking ( 145 ° C. × 3 h) Dissolved by treatment. The obtained solution is heated and filtered through a 0.45 μm filter, and GPC measurement (for example, by HLC-8121 GPC / HT manufactured by Tosoh Corporation) is performed. For example, two TSKgel GMH _HR- HHT (7.8 mmφ × 30 cm) columns are used as the column, and orthodichlorobenzene is used at 1.0 ml / min as the eluent. For example, the weight average molecular weight and the degree of dispersion can be determined by data processing using GPC-8020 manufactured by Tosoh Corporation.

  A metallocene catalyst is preferred as a propylene-ethylene copolymer synthesis catalyst in that the dispersity Mw / Mn can be lowered.

  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.

  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 so that the internal pressure is 0.1 MPa or more may cause the laminate roll to be soiled by bleeding because the support and the protective layer are in close contact with each other. In, since the protective layer (C) is a propylene-based copolymer film, bleeding can be suppressed. The internal pressure applied to the core portion of the dry film resist roll in the present invention 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. 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), but in addition to these, any layer (for example, a cushion layer and 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 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 of the present invention described above, and exposing the photosensitive resin layer. A process for producing a conductor pattern, comprising: an exposure process for developing, a development process for developing a photosensitive resin layer after the exposure to form a resist pattern, and a conductor pattern formation process for etching or plating a substrate on which the resist pattern is formed I will provide a.

  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>
According to the present invention, various members on which the above conductor pattern is formed can be manufactured. Specifically, using the dry film resist roll of the present invention described above, a laminating step for forming a photosensitive resin layer on a substrate that is a copper-clad laminate or a flexible substrate, and an exposing step for exposing the photosensitive resin layer By a method including a development step of developing the photosensitive resin layer after the exposure to form a resist pattern, and a wiring formation step of etching or plating the substrate on which the resist pattern is formed and then peeling the resist pattern, A printed wiring board can be manufactured.

  The printed wiring board manufacturing method 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 resist pattern forming method described above.

[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% by 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 example of a member that can be manufactured according to the present invention is a lead frame. Specifically, using the dry film resist roll of the present invention described above, a laminating step for forming a photosensitive resin layer on a substrate that is a metal plate, an exposing step for exposing the photosensitive resin layer, and a post-exposure step A lead frame can be manufactured by a method including a developing step of developing a photosensitive resin layer to form a resist pattern, and a lead frame forming step of etching the substrate on which the resist pattern is formed and then peeling the resist pattern. .

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

[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 a substrate having an uneven pattern>
Another example of a member that can be produced according to the present invention is a substrate having a concavo-convex pattern. Specifically, using the dry film resist roll of the present invention described above, a laminating step for forming a photosensitive resin layer on a substrate, an exposing step for exposing the photosensitive resin layer, and a photosensitive resin layer after the exposure A substrate having a concavo-convex pattern by a development step of developing a resist pattern to form a resist pattern, and a method including a concavo-convex pattern formation step of processing the substrate on which the resist pattern is formed by a sandblasting method and then peeling the resist pattern Can be manufactured.

  The manufacturing method of the base material which has said uneven | corrugated pattern further includes an uneven | corrugated pattern formation process, after forming a resist pattern with 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 or the like 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 example of a member that can be manufactured according to the present invention is a semiconductor package. Specifically, using the dry film resist roll of the present invention described above, a laminating process for forming a photosensitive resin layer on a substrate, which is a wafer on which circuit formation as an LSI has been completed, and exposing the photosensitive resin layer By a method including an exposure step, a development step of developing the exposed photosensitive resin layer to form a resist pattern, and a package forming step of plating the substrate on which the resist pattern is formed and then peeling the resist pattern A semiconductor package can be manufactured.

  The semiconductor package manufacturing method described above further includes the following steps after a resist pattern is formed by the above-described resist pattern forming method using a wafer on 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 to 3 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.

  Subsequently, in Examples 1-5 as a protective layer (C) (protective film) on the surface of the photosensitive resin layer (B) on which the support (A) is not laminated, a propylene-based copolymer film ( Propylene-ethylene copolymer (polymerization ratio = 100: 3 (mol); trade name: WINTEC (manufactured by Nippon Polypro Co., Ltd.)), low-density polyethylene (LDPE) film (trade name GF-818) in Comparative Examples 1-5 Tamapoly Co., Ltd.) and Comparative Example 6 were laminated with biaxially stretched polypropylene film (E200A; manufactured by Oji Specialty Paper Co., Ltd.) to obtain a dry film resist. Judgment was made based on whether or not it was turned on.

  Next, the obtained dry film resist was wound around a core 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), and the photosensitive resin layer (B) 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) Sensitivity Evaluation A substrate for sensitivity and resolution evaluation 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.

(2) Resolution Evaluation The substrate for resolution evaluation that had passed 15 minutes after lamination was exposed through a line pattern mask having a ratio of 1: 1 between the exposed area and the unexposed area. 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.

(3) Adhesion Evaluation The substrate for sensitivity and resolution evaluation 15 minutes after lamination was exposed through a line pattern mask having a ratio of 1: 1 between the exposed area and the unexposed area. 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.

(4) Bleed-out evaluation (acceleration test)
First, five dry film resists were cut out to 15 × 20 cm, and 3 to 4 alphabets were written on the protective film with a thin sign pen (trade name: Mackey Care, manufactured by Zebra Corporation) in a size of about 1 cm square. Five layers of this dry film resist are stacked and sandwiched between two glass plates (30 cm × 20 cm × 2 mm), and a 4.5 kg weight is placed thereon, and then in an environment of 50 ° C. and 60% RH for 24 hours. Stored. After storage, remove the film, observe the written alphabet for bleeding, and rank as follows:
○: Alphabet is not smudged ×: Alphabet smudge is visually observable XX: Alphabet is bleed vigorously (that is, the smear encloses all outlines)

(5) Internal pressure of roll 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. The evaluation results of Examples 1 to 5 and Comparative Examples 1 to 6 are shown in Table 2 below.

  The present invention includes, for example, manufacture of printed wiring boards, manufacture of lead frames for mounting IC chips, precision processing of metal foil such as manufacture of metal masks, manufacture of packages such as BGA and CSP, manufacture of tape substrates such as COF and TAB, and semiconductor bumps. Can be used for the manufacture of barrier ribs for flat panel displays such as electromagnetic wave shields, and the like.

Claims (7)

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,
A dry film resist roll, wherein the protective layer (C) is a propylene-based copolymer film.   The dry film resist roll according to claim 1, wherein the propylene-based copolymer is a copolymer of 1) propylene and 2) ethylene and / or a C4 to C18 α-olefin.   The dry film resist roll according to claim 1 or 2, wherein the propylene-based copolymer is a propylene-ethylene copolymer.   The dry film according to any one of claims 1 to 3, comprising a compound having a molecular weight of 600 or less as the addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule (b). Resist roll. 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 , A is C ₂ H ₄ , B is C ₃ H ₆ , and n ₁ and n ₃ are each independently 1 to 29 N ₁ + n ₃ is an integer of 2-30, n ₂ and n ₄ are each independently an integer of 0-29, and n ₂ + n ₄ 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 of any one of Claims 1-4 containing the photopolymerizable unsaturated compound represented by these. A laminating step of forming a photosensitive resin layer on a substrate using the dry film resist roll according to any one of claims 1 to 5,
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. Using the dry film resist roll according to any one of claims 1 to 5, a laminating step for forming a photosensitive resin layer on a substrate that is a metal plate or a metal film insulating plate,
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.