JP5411521B2 - Photosensitive resin laminate - Google Patents

Description

The present invention relates to a photosensitive resin composition that can be developed with an alkaline aqueous solution, a photosensitive resin laminate in which the photosensitive resin composition is laminated on a support, and a resist pattern on a substrate using the photosensitive resin laminate. The present invention relates to a method for forming the resist pattern and an application of the resist pattern.
More specifically, the present invention relates to the manufacture of printed wiring boards, the manufacture of flexible printed wiring boards, the manufacture of lead frames for IC chip mounting (hereinafter referred to as lead frames), the precision processing of metal foils such as the manufacture of metal masks, BGA (ball Tape substrate represented by semiconductor package manufacturing such as grid array), 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 that provides a resist pattern suitable for manufacturing members such as ITO bumps, address electrodes or electromagnetic wave shields in the field of flat panel display and semiconductor bumps.

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

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

A method for producing a printed wiring board using the dry film resist will be briefly described below.
First, when the dry film resist has a protective layer such as a polyethylene film, it is peeled off from the photosensitive resin layer. Next, the photosensitive resin layer and the support are laminated on a substrate such as a copper clad laminate using a laminator so that the substrate, the photosensitive resin layer, and the support are in this order. Next, the exposed portion is polymerized and cured by exposing the photosensitive resin layer with ultraviolet rays such as i rays (365 nm) emitted from an ultrahigh pressure mercury lamp through a photomask having a wiring pattern. Next, the support made of polyethylene terephthalate or the like is peeled off. Next, a non-exposed portion of the photosensitive resin layer is dissolved or dispersed and removed by a developing solution such as an aqueous solution having weak alkalinity to form a resist pattern on the substrate. Next, a known etching process or pattern plating process is performed using the formed resist pattern as a protective mask. In the method of removing the metal portion by etching, the metal in the hole is prevented from being etched by covering the through hole (through hole) of the substrate and the via hole for interlayer connection with a cured resist film. This construction method is called a tenting method. 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 aqueous alkali solution such as sodium hydroxide to produce a substrate having a conductor pattern, that is, a printed wiring board.

  In order to produce printed wiring boards with high yield, it is necessary to improve the embedding property of the photosensitive resin composition on the uneven surface of the base material. In the following Patent Document 1, Patent Document 2, etc., a vacuum laminator is used. It is used. In this case, if the tackiness between the photosensitive layer and the substrate becomes strong, bubbles remain in the concavo-convex portion even when placed under reduced pressure. As means for solving this, in the invention described in the following Patent Document 3, by using a film having a rough surface for the protective layer, the surface roughness is given to the photosensitive resin composition layer, so that it can be applied during vacuum lamination. However, Patent Document 3 does not describe anything about the performance of the dry film resist such as sensitivity and resist pattern which are actually important in the production of printed wiring boards. On the other hand, increasing the exposure sensitivity of the dry film resist is very significant from the viewpoint of productivity.

JP-A-53-31670 Japanese Patent Laid-Open No. 51-63702 JP 2000-147755 A

  The present invention relates to a photosensitive resin laminate having an effect of improving sensitivity by laminating unevenness of a substrate without bubbles, a method of forming a resist pattern on a substrate using the photosensitive resin laminate, and uses of the resist pattern. The issue is to provide.

The above-described object can be achieved by the following solution means of the present invention.
[1] A photosensitive resin laminate obtained by sequentially laminating a photosensitive resin layer and a protective layer on a support, and the protective layer has an average roughness (Ra) of a surface in contact with the photosensitive resin layer. 0.5 μm or more, and the photosensitive resin layer comprises (a) 20 to 90% by mass of a carboxyl group-containing thermoplastic copolymer, and (b) at least one polymerizable terminal ethylenically unsaturated group in the molecule. A dry film resist containing 5 to 75% by mass of an addition polymerizable monomer having (1) and 0.01 to 30% by mass of a photopolymerization initiator, and (c) a hexaarylbisimidazole derivative as the photopolymerization initiator The photosensitive resin laminated body characterized by including.

  [2] The photosensitive resin laminate according to [1], wherein the photosensitive resin layer includes (d) an N-arylamino acid.

｛式中、Ｒ_１及びＲ_２は、Ｈ又はＣＨ_３であり、これらは同一であっても相違してもよく、ｎ_１、ｎ_２及びｎ_３は、それぞれ独立に、３〜２０の整数である。｝で表される光重合可能な不飽和化合物、及び一般式（ＩＩ）：

｛式中、Ｒ_３及びＲ_４は、Ｈ又はＣＨ_３であり、これらは同一であっても相違してもよく、Ａは、Ｃ_２Ｈ_４であり、Ｂは、Ｃ_３Ｈ_６であり、ｎ_４＋ｎ_５は、２〜３０の整数であり、ｎ_６＋ｎ_７は、０〜３０の整数であり、ｎ_４及びｎ_５は、それぞれ独立に、１〜２９の整数であり、ｎ_６及びｎ_７は、それぞれ独立に、０〜２９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）−及び−（Ｂ−Ｏ）−のいずれがビスフェノールＡ基側でもよい。｝で表される光重合可能な不飽和化合物から成る群から選ばれる少なくとも一種の化合物を含有する、前記［１］又は［２］に記載の感光性樹脂積層体。 [3] The addition polymerization monomer (b) having at least one polymerizable terminal ethylenically unsaturated group in the molecule is represented by the following general formula (I):

{Wherein R ₁ and R ₂ are H or CH ₃ , which may be the same or different, and n ₁ , n ₂ and n ₃ are each independently an integer of 3 to 20 It is. } The photopolymerizable unsaturated compound represented by the general formula (II):

{Wherein R ₃ and R ₄ are H or CH ₃ , which may be the same or different, A is C ₂ H ₄ and B is C ₃ H ₆ , N ₄ + n ₅ is an integer of 2 to 30, n ₆ + n ₇ is an integer of 0 to 30, n ₄ and n ₅ are each independently an integer of 1 to 29, and n ₆ And n ₇ are each independently an integer of 0 to 29, and the sequence of the repeating units of-(AO)-and-(B-O)-may be random or block. In the case of a block, either-(A-O)-or-(B-O)-may be on the bisphenol A group side. } The photosensitive resin laminate according to [1] or [2] above, which contains at least one compound selected from the group consisting of photopolymerizable unsaturated compounds represented by:

  [4] A resist pattern including a laminating process, an exposing process, and a developing process for forming a photosensitive resin layer on a substrate using the photosensitive resin laminate according to any one of [1] to [3]. Forming method.

  [5] A method for producing a conductor pattern, comprising: etching or plating a substrate on which a resist pattern is formed using a metal plate or a metal film insulating plate as a substrate in the method according to [4].

  [6] A method for producing a printed wiring board, comprising etching or plating a substrate on which a resist pattern is formed using a copper-clad laminate or a flexible substrate as the substrate in the method described in [4].

  [7] A method for manufacturing a lead frame, comprising: etching a substrate on which a resist pattern is formed using a metal plate as a substrate in the method according to [4], and then peeling the resist pattern.

  [8] The method according to [4], wherein a substrate on which a resist pattern is formed using a glass substrate coated with glass rib paste as a substrate is processed by a sandblasting method, and then the resist pattern is peeled off. The manufacturing method of the base material which has an uneven | corrugated pattern.

  [9] A semiconductor package characterized by plating a substrate on which a resist pattern is formed using a wafer on which circuit formation as an LSI has been completed as a substrate in the method described in [4], and then peeling the resist pattern Manufacturing method.

  The present invention relates to a photosensitive resin laminate having an effect of improving sensitivity by laminating unevenness of a substrate without bubbles, a method of forming a resist pattern on a substrate using the photosensitive resin laminate, and uses of the resist pattern. And can be suitably used for manufacturing a printed wiring board, a lead frame, a semiconductor package, and a flat display.

Hereinafter, the present invention will be specifically described.
<Support>
The support of the present invention is a film for supporting the photosensitive resin layer of the present invention, and 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. , Polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film and the like. These films can be stretched if necessary. The haze is preferably 5 or less. The thinner the film, the more advantageous in terms of image forming property and economic efficiency, but a film having a thickness of 10 to 30 μm is preferably used because the strength needs to be maintained.

<Photosensitive resin layer>
In the photosensitive resin layer of the present invention, (a) 20 to 90% by mass of a carboxyl group-containing thermoplastic copolymer, (b) addition polymerization having at least one polymerizable terminal ethylenically unsaturated group in the molecule. A dry film resist containing 5 to 75% by weight of a polymerizable monomer and (c) 0.01 to 30% by weight of a photopolymerization initiator, and further comprising (c) a hexaarylbis Contains an imidazole derivative as an essential component.

(A) Thermoplastic copolymer The photosensitive resin composition of the present invention comprises (a) a carboxyl group-containing monomer as a copolymerization component, an acid equivalent of 100 to 600, and a weight average molecular weight of 5,000 to 500. , 000 thermoplastic copolymer.

  The carboxyl group in the thermoplastic copolymer is necessary for the photosensitive resin composition to have developability and releasability with respect to a developer and a release solution made of an alkaline aqueous solution. The acid equivalent is preferably 100 to 600, more preferably 250 to 450. From the viewpoint of ensuring compatibility with other components in the solvent or composition, particularly (b) addition polymerizable monomer described later, the acid equivalent is 100 or more, and maintain developability and peelability. From this viewpoint, it is 600 or less. Here, an acid equivalent means the mass (gram) of the thermoplastic copolymer which has a 1 equivalent carboxyl group in it. The acid equivalent is measured by potentiometric titration with a 0.1 mol / L NaOH aqueous solution using a Hiranuma Reporting Titrator (COM-555).

  The weight average molecular weight of the thermoplastic polymer of the present invention is 5,000 to 500,000. It is 5,000 or more from the viewpoint of maintaining the thickness of the dry film resist uniformly and obtaining resistance to the developer, and 500,000 or less from the viewpoint of maintaining developability. More preferably, the weight average molecular weight is 20,000 to 100,000. The weight average molecular weight in this case is a weight average molecular weight measured by gel permeation chromatography (GPC) using a 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

The thermoplastic copolymer is a copolymer comprising at least one of the first monomers described later, or at least one of the first monomers and a second monomer described later. It is preferable that the copolymer is composed of at least one body.
The first monomer is a monomer containing a carboxyl group in the molecule. Examples include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is particularly preferable. Here, (meth) acryl indicates acryl or methacryl. The same applies hereinafter.

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

  The amount of the thermoplastic polymer contained in the photosensitive resin composition is preferably in the range of 20 to 90% by mass, more preferably in the range of 25 to 70% by mass. This amount is 20% by mass or more from the viewpoint of maintaining alkali developability, and is 90% by mass or less from the viewpoint that the resist pattern formed by exposure sufficiently exhibits the performance as a resist.

｛式中、Ｒ_１及びＲ_２は、Ｈ又はＣＨ_３であり、これらは同一であっても相違してもよく、ｎ_１、ｎ_２及びｎ_３は、それぞれ独立に、３〜２０の整数である。｝で表される光重合可能な不飽和化合物、及び一般式（ＩＩ）：

｛式中、Ｒ_３及びＲ_４は、Ｈ又はＣＨ_３であり、これらは同一であっても相違してもよく、Ａは、Ｃ_２Ｈ_４であり、Ｂは、Ｃ_３Ｈ_６であり、ｎ_４＋ｎ_５は、２〜３０の整数であり、ｎ_６＋ｎ_７は、０〜３０の整数であり、ｎ_４及びｎ_５は、それぞれ独立に、１〜２９の整数であり、ｎ_６及びｎ_７は、それぞれ独立に、０〜２９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）−及び−（Ｂ−Ｏ）−のいずれがビスフェノールＡ基側でもよい。｝で表される光重合可能な不飽和化合物から成る群から選ばれる少なくとも一種の化合物を含有することが好ましい。 (B) Addition polymerizable monomer (b) The addition polymerizable monomer having at least one terminal ethylenically unsaturated group used in the photosensitive resin composition is represented by the following general formula from the viewpoint of high resolution and edge fuse properties. (I):

{Wherein R ₁ and R ₂ are H or CH ₃ , which may be the same or different, and n ₁ , n ₂ and n ₃ are each independently an integer of 3 to 20 It is. } The photopolymerizable unsaturated compound represented by the general formula (II):

{Wherein R ₃ and R ₄ are H or CH ₃ , which may be the same or different, A is C ₂ H ₄ and B is C ₃ H ₆ , N ₄ + n ₅ is an integer of 2 to 30, n ₆ + n ₇ is an integer of 0 to 30, n ₄ and n ₅ are each independently an integer of 1 to 29, and n ₆ And n ₇ are each independently an integer of 0 to 29, and the sequence of the repeating units of-(AO)-and-(B-O)-may be random or block. In the case of a block, either-(A-O)-or-(B-O)-may be on the bisphenol A group side. } It is preferable to contain at least one compound selected from the group consisting of photopolymerizable unsaturated compounds represented by:

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. It is 3 or more from the viewpoint of improving tenting properties, and 20 or less from the viewpoint of improving sensitivity and resolution. More preferably, n ₁ and n ₃ are 3 or more and 10 or less, and n ₂ is 5 or more and 15 or less.

In the compound represented by the general formula (II), the lower limit of n ₄ + n ₅ + n ₆ + n ₇ is preferably 2 or more, and the upper limit is preferably 40 or less. These values are preferably 2 or more from the viewpoint of flexibility of the effect film and tenting properties, and these values are preferably 40 or less from the viewpoint of the effect on resolution. As a specific example represented by the above general formula (II), polyethylene glycol dimethacrylate (NK ester BPE- manufactured by Shin-Nakamura Chemical Co., Ltd.) having an average of 2 moles of ethylene oxide added to both ends of bisphenol A, respectively. 200) and bisphenol A at both ends, an average of 5 moles of ethylene oxide added to polyethylene glycol dimethacrylate (NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.) and bisphenol A at both ends, respectively. Polyalkylene glycols with an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide added to both ends of a polyalkylene glycol dimethacrylate and bisphenol A with 6 moles of ethylene oxide and an average of 2 moles of propylene oxide added, respectively. Call of dimethacrylate and the like.

  The amount of the photopolymerizable unsaturated compound represented by the general formula (I) is preferably 3% by mass or more and 70% by mass or less. It is 3% by mass or more from the viewpoint of improving sensitivity, resolution, adhesion and tenting, and 70% by mass or less from the point of suppressing edge fuse. More preferably, they are 3 mass% or more and 50 mass% or less, More preferably, they are 3 mass% or more and 30 mass% or less.

  The amount of the photopolymerizable unsaturated compound represented by the general formula (II) is preferably 3% by mass or more from the viewpoint of sensitivity, and preferably 70% by mass or less from the viewpoint of edge fuse. More preferably, it is 10-65 mass%, More preferably, it is 15-55 mass%. As the addition polymerizable monomer (b) having at least one terminal ethylenically unsaturated group used in the photosensitive resin composition of the present invention, in addition to the compound represented by the above general formula (1) or general formula (II) Also known compounds having at least one terminal ethylenically unsaturated group can be used.

  For example, 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxyhexaethylene glycol acrylate, a reaction product of a half ester compound of phthalic anhydride and 2-hydroxypropyl acrylate and propylene oxide (Nippon Shokubai Chemical Co., Ltd., trade name OE-A 200), 4-normal octylphenoxypentapropylene glycol acrylate, 1,6-hexanediol (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di Polyoxyalkylene glycol di (meth) acrylates such as (meth) acrylate and polyethylene glycol di (meth) acrylate, 2-di (p-hydroxy) Phenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, 2,2-bis (4-methacryloxypentaethoxyphenyl) propane And polyfunctional group (meth) acrylates containing urethane groups such as urethanized products of hexamethylene diisocyanate and nonapropylene glycol monomethacrylate, polyfunctional (meth) acrylates of isocyanuric acid ester compounds, and the like. These may be used alone or in combination of two or more.

  (B) The amount of the addition polymerizable monomer having at least one terminal ethylenically unsaturated group is in the range of 5 to 75% by mass, and more preferably in the range of 15 to 70% by mass. This amount is 5% by mass or more from the viewpoint of suppressing poor curing and development time delay, and is 75% by mass or less from the viewpoint of suppressing cold flow and effective resist peeling delay.

(C) Photopolymerization initiator (c) The amount of the photopolymerization initiator is in the range of 0.01 to 30% by mass, and a more preferable range is 0.05 to 10% by mass. From the viewpoint of obtaining sufficient sensitivity, the amount of the photopolymerization initiator is preferably 0.01% by mass or more, and sufficiently transmits light to the bottom surface of the resist to obtain good high resolution and adhesion. In view of the above, 30% by mass or less is preferable.

  In the present invention, (c) a hexaarylbisimidazole derivative is included as an essential component as a photopolymerization initiator. The hexaarylbisimidazole derivative is effective in that it provides a sensitivity improvement effect when combined with a protective layer described later. Examples of hexaarylbisimidazole (hereinafter, triarylimidazole dimer) include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer (hereinafter, 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'-bis- (2-fluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3-difluoro Methylphenyl) -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-methoxy Phenyl) -imidazolyl dimer, 2,2′-bis- (2,6-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2, 2'-bis- (2,3,4-triflu Orophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,5-trifluorophenyl) -4,4 ′ , 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,6-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-tetrafur Rophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,4,6-tetrafluorophenyl) -4, 4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, and 2,2'-bis- (2,3,4,5,6-pentafluorophenyl) -4,4' , 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer and the like. In particular, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer is a photopolymerization initiator having a high effect on resolution and strength of a cured film, and is preferably used. These may be used alone or in combination of two or more.

  (C) It is a preferred embodiment of the present invention to contain an acridine compound or a pyrazoline compound as a photopolymerization initiator. 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, among which 9-phenylacridine is desirable.

  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, 3-chloro-2-methylanthraquinone, benzophenone , Aromatic ketones such as Michler's ketone [4,4′-bis (dimethylamino) benzophenone], 4,4′-bis (diethylamino) benzophenone, benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, ethylbenzo Benzoin ethers such as ethylene, benzyl dimethyl ketal, benzyl diethyl ketal, combinations of thioxanthones and alkylaminobenzoic acid, 1-phenyl-1,2-propanedione-2-O-benzoin oxime, 1-phenyl-1,2 -Oxime esters such as 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 ethyl dimethylaminobenzoate, isopropylthioxanthone and dimethylaminobenzoic acid. A combination with ethyl is mentioned.

(D) N-aryl amino acid (d) It is preferable to contain 0.001-1.0 mass% of N-aryl amino acids in the photosensitive resin layer of this invention, More preferably, N-aryl amino acid is 0. 0.05 to 0.5% by mass. From the viewpoint of improving sensitivity, 0.01% by mass or more is preferable, and from the viewpoint of obtaining good resolution, 1.0% by mass or less is preferable.
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.

  As other components, coloring substances such as dyes and pigments can be employed in addition to the components described above. Examples of such coloring substances include phthalocyanine green, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, basic blue 20, diamond green, and the like.

  Moreover, you may add a color former in the photosensitive resin composition so that a visible image can be given by exposure. Examples of such coloring dyes include leuco dyes, 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, chlorinated triazine compounds and the like.

The amount of the coloring substance and the color former in the photosensitive resin composition is preferably 0.01 to 10% by mass, respectively. The amount is preferably 0.01% by mass or more from the viewpoint that sufficient colorability (coloring property) can be recognized, and 10% by mass or less from the viewpoint of having a contrast between the exposed part and the unexposed part and maintaining storage stability.
Furthermore, in order to improve the thermal stability and storage stability of the photosensitive resin composition, the photosensitive resin composition is at least one selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles. It is preferable to contain the above compounds.

  Examples of such radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2 Examples include '-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 amount of radical polymerization inhibitors, benzotriazoles and carboxybenzotriazoles is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass. This amount is preferably 0.01% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and more preferably 3% by mass or less from the viewpoint of maintaining sensitivity.

  Moreover, you may make the photosensitive resin layer of this invention contain a plasticizer as needed. Examples of such additives include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl Ethers, polyoxypropylene monoethyl ether, glycol esters such as polyoxyethylene polyoxypropylene monoethyl ether, phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, citric acid Tributyl, triethyl citrate, triethyl acetylcitrate, tri-n-propyl acetylcitrate, tri-n-acetylcitrate Chill, and the like.

It is preferable that content of the plasticizer in the photosensitive resin composition is 5-50 mass%, More preferably, it is 5-30 mass%. 5 mass% or more is preferable from a viewpoint of suppressing the delay of image development time and providing a softness | flexibility to a cured film, On the other hand, 50 mass% or less is preferable from a viewpoint of suppressing insufficient hardening and cold flow.
The thickness of the photosensitive resin layer of the present invention is preferably 5 to 100 μm, more preferably 7 to 60 μm. As the thickness is thinner, the resolution is improved, and as the thickness is increased, the film strength is improved. Therefore, the thickness can be appropriately selected according to the application.

<Protective layer>
The thickness of the protective layer of the present invention is preferably 10 μm or more and 100 μm or less, and the center line average roughness (Ra) is preferably 0.5 μm or more in terms of surface roughness.
The centerline average roughness (Ra) and the maximum height (Rmax) in the surface roughness mentioned here are the centerline average roughness and the maximum height measured with an ultra-deep shape measuring microscope (manufactured by VK-8550 KEYENCE). Say it. The surface roughness is defined by JIS B0601-1994.
The photosensitive resin composition contains a photopolymerization initiator containing a hexaarylbisimidazole derivative, and is obtained by using a protective layer having a surface roughness centerline average roughness of 0.5 μm or more as a protective layer to be laminated. The photosensitive resin laminate has an effect of improving sensitivity as well as laminating unevenness without bubbles. Furthermore, the photosensitive resin laminate thus obtained is excellent in resolution without being affected by the unevenness of the protective layer.

  In addition, 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. For example, a polyethylene film and a polypropylene film can be preferably used as the protective layer. A method of preparing a dry film resist by sequentially laminating a support, a photosensitive resin layer, and a protective layer can be performed by a conventionally known method. For example, the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent that dissolves them to form a uniform solution, and is first coated on a support using a bar coater or roll coater, dried, and then supported. A photosensitive resin layer made of a photosensitive resin composition is laminated on the body. Next, a dry film resist can be produced by laminating a protective layer on the photosensitive resin layer.

<Resist pattern formation method>
A resist pattern using a dry film resist can be formed by a process including a laminating process, an exposing process, and a developing process. An example of a specific method is shown below.
First, a laminating process is performed using a laminator. In the dry film resist of the present invention, after removing the protective layer, the photosensitive resin layer is laminated on the substrate and brought into close contact by heating and pressurization. It is effective to carry out 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.

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

Next, a developing process is performed using a developing device. After the exposure, if the support is on the photosensitive resin layer, the support 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 according to 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. A surface active agent, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution. 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.

<Conductor Pattern Manufacturing Method / Printed Wiring Board Manufacturing Method>
The conductor pattern manufacturing method is performed by using a metal plate or a metal film insulating plate as a substrate, forming a resist pattern by the above-described resist pattern forming method, and then performing the following steps.
First, a step of forming a conductor pattern on the copper surface of the substrate exposed by development using a known method such as an etching method or a plating method is performed.
Thereafter, the resist pattern is peeled off from the substrate with an aqueous solution having alkalinity stronger than that of the developer to obtain a desired printed wiring board. The alkaline aqueous solution for peeling (hereinafter also referred to as “peeling solution”) is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of 2 to 5% by mass is generally used. It is 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 in a peeling process is the range of 40-70 degreeC.
The manufacturing method of a printed wiring board is performed by using the above-mentioned etching process or the process of plating, using a copper clad laminated board or a flexible substrate as a board | substrate.

<Lead frame manufacturing method>
The lead frame manufacturing method of the present invention is performed by performing the following steps after forming a resist pattern on a metal plate such as copper, copper alloy, iron-based alloy or the like as a substrate by the above-described resist pattern forming method.
First, a step of etching the substrate exposed by development to form a conductor pattern is performed. Then, the peeling process which peels a resist pattern with the method similar to the manufacturing method of the above-mentioned printed wiring board is performed, and a desired lead frame is obtained.

<Manufacturing method of substrate having concave / convex pattern>
The resist pattern produced by the above-mentioned resist pattern forming method can be used as a protective mask member when processing a 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, a blasting material is sprayed on the formed resist pattern to be cut to a desired depth, and a resist pattern portion remaining on the substrate is removed from the substrate with an alkali stripping solution or the like, and then on the substrate. It can be set as the base material which has a fine uneven | corrugated pattern. The blasting material used for the above-mentioned sandblasting process may be a known material, for example, fine particles of about 2 to 100 μm such as SiC, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO, glass, stainless steel and the like.

<Semiconductor package manufacturing method>
A semiconductor package manufacturing method is performed by forming a resist pattern on a wafer on which a circuit as an LSI has been formed as a substrate by the above-described resist pattern forming method, and then performing the following steps.
First, a step of forming a conductor pattern by performing columnar plating such as copper or solder on the opening exposed by development is performed. Thereafter, a peeling process for peeling the resist pattern by the same method as the printed wiring board manufacturing method described above is performed, and further, a thin metal layer other than the columnar plating is removed by etching, thereby obtaining a desired semiconductor. Get the package.

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 photosensitive resin laminates in Examples 1 to 4 and Comparative Examples 1 to 6 were produced as follows.

<Preparation of dry film resist>
Prepare the compounds shown in Table 1 below, and mix the photosensitive resin compositions having the composition ratios shown in Table 2 below with a solvent that dissolves them. The uniform solution was uniformly applied to the support layer using a bar coater on the surface of a polyethylene terephthalate film having a thickness of 16 μm as a support layer, and dried to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 40 μm.
Examples of the solvent include ketones typified by methyl ethyl ketone (MEK), and alcohols typified by methanol, ethanol, and isopropanol. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition applied on the support is 500 to 4,000 mPa at 25 ° C.
Next, a polyethylene film having a center line average roughness (Ra) shown in Table 2 below is laminated as a protective layer (protective film) on the surface of the photosensitive resin layer on which the support layer is not laminated to form a dry film resist. Obtained.

<Board surface preparation>
As a substrate used for measuring etching solution resistance, resolution, and adhesion, a 1.2 mm thick copper clad laminate on which 35 μm rolled copper foil is laminated, and the surface is subjected to wet buffol polishing (manufactured by 3M Co., Ltd., Scotch Bright). (Registered trademark) HD # 600, twice).
A substrate subjected to jet scrub polishing (manufactured by Nippon Grinding Abrasive Co., Ltd., Sac Random A (registered trademark) # F220P) was prepared as a substrate for evaluation.

<Laminate>
While peeling the polyethylene film of the photosensitive resin laminate, roll the photosensitive resin layer on a copper-clad laminate pre-heated to 60 ° C. using a hot roll laminator (AL-70, manufactured by Asahi Kasei Co., Ltd.). Lamination was performed at 105 ° C. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.

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

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

2. Evaluation Method (1) Sensitivity Evaluation 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 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 30 μm or less;
○: Resolution value of more than 30 μm and 35 μm or less;
(Triangle | delta): The value of resolution exceeds 35 micrometers.

(3) Adhesion Evaluation The substrate for sensitivity and resolution evaluation 15 minutes after lamination was exposed through a line pattern mask in which the width of the exposed area and the unexposed area was 1: 1. Development was 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 35 μm or less;
○: Adhesiveness value is over 35 μm and 40 μm or less
(Triangle | delta): The value of adhesiveness exceeds 40 micrometers.

  The evaluation results of Examples 1 to 4 and Comparative Examples 1 to 6 are shown in Table 2 below.

  The present invention manufactures printed wiring boards, IC chip mounting lead frames, metal foil precision processing such as metal mask manufacturing, BGA and CSP package manufacturing, COF and TAB tape substrate manufacturing, and semiconductor bump manufacturing. It can be used in a method of manufacturing a partition of a flat panel display such as an ITO electrode, an address electrode, and an electromagnetic wave shield.

Claims (9)

A photosensitive resin laminate obtained by sequentially laminating a photosensitive resin layer and a protective layer on a support, and the protective layer has an average roughness (Ra) of a surface in contact with the photosensitive resin layer of 0.5 μm. The photosensitive resin layer is (a) 20 to 90% by mass of a carboxyl group-containing thermoplastic copolymer containing styrene as a monomer component , and (b) at least one polymerizable in the molecule. A dry film resist comprising 5 to 75% by mass of an addition polymerizable monomer having a terminal ethylenically unsaturated group and (c) 0.01 to 30% by mass of a photopolymerization initiator, and (c) the photopolymerization initiator A photosensitive resin laminate comprising a hexaarylbisimidazole derivative as   The photosensitive resin laminated body of Claim 1 which contains (d) N-arylamino acid in the said photosensitive resin layer. (B) The addition polymerizable monomer having at least one polymerizable terminal ethylenically unsaturated group in the molecule is represented by the following general formula (I):

{Wherein R ₁ and R ₂ are H or CH ₃ , which may be the same or different, and n ₁ , n ₂ and n ₃ are each independently an integer of 3 to 20 It is. } The photopolymerizable unsaturated compound represented by the general formula (II):

{Wherein R ₃ and R ₄ are H or CH ₃ , which may be the same or different, A is C ₂ H ₄ and B is C ₃ H ₆ , N ₄ + n ₅ is an integer of 2 to 30, n ₆ + n ₇ is an integer of 0 to 30, n ₄ and n ₅ are each independently an integer of 1 to 29, and n ₆ And n ₇ are each independently an integer of 0 to 29, and the sequence of the repeating units of-(AO)-and-(B-O)-may be random or block. In the case of a block, either-(A-O)-or-(B-O)-may be on the bisphenol A group side. } The photosensitive resin laminated body of Claim 1 or 2 containing the at least 1 type of compound chosen from the group which consists of a photopolymerizable unsaturated compound represented by these.   A resist pattern forming method comprising a laminating step, an exposing step, and a developing step of forming a photosensitive resin layer on a substrate using the photosensitive resin laminate according to claim 1.   5. A method for producing a conductor pattern, comprising: etching or plating a substrate on which a resist pattern is formed using a metal plate or a metal film insulating plate as the substrate according to claim 4.   5. A method for producing a printed wiring board according to claim 4, wherein a substrate on which a resist pattern is formed using a copper-clad laminate or a flexible substrate as a substrate is etched or plated.   5. A method of manufacturing a lead frame according to claim 4, wherein a substrate on which a resist pattern is formed using a metal plate as a substrate is etched, and then the resist pattern is peeled off.   5. A method according to claim 4, wherein the substrate has a concavo-convex pattern, wherein a substrate on which a resist pattern is formed using a glass substrate coated with a glass rib paste as a substrate is processed by a sandblasting method and then the resist pattern is peeled off. A method for producing a substrate.   5. A method of manufacturing a semiconductor package, comprising: plating a substrate on which a resist pattern is formed using a wafer on which circuit formation as an LSI has been completed as a substrate in the method according to claim 4, and then peeling the resist pattern.