KR20110044270A - Photosensitive resin composition, photosensitive resin laminate, method for forming resist pattern, conductive pattern, printed wiring board, lead frame, base, and method for manufacturing semiconductor package - Google Patents

Abstract

(식 중, R₁ ∼ R₅ 는 각각 독립적으로 H, 아릴기 또는 아릴알킬기이며, 또한 R₁ ∼ R₅ 중 적어도 1 개는 아릴기 또는 아릴알킬기이며, A¹ 은 C₂H₄ 또는 C₃H₆ 이며, n₁ 이 2 이상인 경우 복수의 A¹ 은 서로 동일해도 되고 상이해도 되며, 그리고 n₁ 은 1 ∼ 50 의 정수이다) 로 나타내는 화합물을 함유하는 감광성 수지 조성물을 제공한다.Provided is a photosensitive resin composition that provides excellent resolution, adhesiveness, tentability, and peelability. The present invention is (a) a thermoplastic polymer having an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000 polymerized using at least an α, β-unsaturated carboxyl group-containing monomer as a polymerization component, and (b) at least one polymerizable molecule. An addition polymerizable monomer having an ethylenically unsaturated bond, (c) a photopolymerization initiator, and (d) the following general formula (I):

(Wherein, R ₁ to R ₅ are each independently H, an aryl group or an arylalkyl group, and at least one of R ₁ to R ₅ is an aryl group or an arylalkyl group, and A ¹ is C ₂ H ₄ or C ₃ It is H <_6> , and when n <_1> is 2 or more, some A <^1> may mutually be same or different, and n <_1> is an integer of 1-50), The photosensitive resin composition containing the compound represented by this is provided.

Description

PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE RESIN LAMINATE, METHOD FOR FORMING RESIST PATTERN, CONDUCTIVE PATTERN, PRINTED WIRING BOARD, LEAD FRAME, BASE, AND METHOD FOR MANUFACTURING SEMICONDUCTOR PACKAGE}

The present invention provides a method of forming a resist pattern on a substrate using a photosensitive resin composition which can be developed by an alkaline aqueous solution, a photosensitive resin laminate obtained by laminating the photosensitive resin composition on a support, and the photosensitive resin laminate, and a resist pattern thereof. It relates to the use of. More specifically, manufacturing of printed wiring boards, manufacturing of flexible printed wiring boards, manufacturing of IC chip mounting lead frames (hereinafter simply referred to as lead frames), metal foil precision processing such as metal mask manufacturing, BGA (ball grid array), Manufacture of semiconductor packages such as CSP (chip size package), manufacture of tape substrates represented by TAB (Tape Automated Bonding) or COF (Chip On Film) TECHNICAL FIELD The present invention relates to a photosensitive resin composition that provides a resist pattern suitable for manufacturing a member such as an ITO electrode, an address electrode, or an electromagnetic shield in the field of manufacture or flat panel display.

Conventionally, printed wiring boards are manufactured by the photolithography method. In the photolithography method, a photosensitive resin composition is applied onto a substrate, and pattern exposed, and the polymerized and cured exposed portions of the photosensitive resin composition are removed, and the unexposed portion is removed with a developer to form a resist pattern on the substrate. After the etching or plating is performed to form the conductor pattern, the conductor pattern can be formed on the substrate by peeling off the resist pattern from the substrate.

In the said photolithography method, when apply | coating a photosensitive resin composition on a board | substrate, the method of apply | coating and drying the solution of the photosensitive resin composition to a board | substrate, or the layer which consists of a support body and the photosensitive resin composition (Hereinafter, a "photosensitive resin layer" And the method of laminating | stacking the photosensitive resin laminated body (henceforth a "dry film resist") which laminated | stacked the protective layer sequentially as needed on a board | substrate. And in manufacture of a printed wiring board, the latter dry film resist is used in many cases.

The method of manufacturing a printed wiring board using the said dry film resist is briefly described below. First, when a dry film resist has protective layers, such as a polyethylene film, it peels this from the photosensitive resin layer. Subsequently, the photosensitive resin layer and the support body are laminated | stacked on the board | substrates, such as a copper clad laminated board, in order of the board | substrate, the photosensitive resin layer, and a support body using a laminator. Next, the exposure part is polymerized and hardened | cured by exposing the photosensitive resin layer to ultraviolet rays, such as i line | wire (365 nm) from which ultra-high pressure mercury lamp emits, through the photomask which has a wiring pattern. Next, the support body which consists of polyethylene terephthalate etc. is peeled off. Subsequently, the unexposed part of the photosensitive resin layer is melt | dissolved or disperse | dissolved with developing solutions, such as aqueous solution which has weak alkalinity, and a resist pattern is formed on a board | substrate. Next, a well-known etching process or pattern plating process is performed using the formed resist pattern as a protective mask. In the method of removing a metal part by etching, the metal in the hole is not etched by covering the through hole (through hole) of the substrate or the via hole for interlayer connection with a cured resist film. This method is called tenting method. In the etching process, 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 to prepare a substrate having a conductor pattern, that is, a printed wiring board. It is preferable that peeling speed is fast from a viewpoint of workability, handleability, and productivity.

On the other hand, with the miniaturization of the wiring space | interval in the recent printed wiring board, the demand for high resolution has increased in dry film resist. In the tenting method and the plating method, the adhesion between the resist and the copper is important in order not to infiltrate the etching solution and the plating solution between the resist and the copper, but there is a problem in that the peeling time increases with the improvement of the adhesion.

Patent Document 1 describes a photosensitive resin composition containing a chain copolymer of ethylene oxide and propylene oxide in order to improve the tentability while maintaining the high resolution and high adhesion of the photosensitive resin composition. It is not.

Japanese Unexamined Patent Publication No. 2004-20726

Therefore, as the photosensitive resin composition for dry films, the photosensitive resin composition which is excellent in resolution, adhesiveness, and tentability, and which contributes to the improvement of workability, handleability, and productivity largely is not yet provided.

This invention is excellent in the resolution, adhesiveness, and tentability, the photosensitive resin composition which has the outstanding peelability by the aqueous alkali solution of a cured resist film, the photosensitive resin laminated body using this photosensitive resin composition, and the photosensitive resin laminated body on the board | substrate using the photosensitive resin laminated body. An object of the present invention is to provide a resist pattern method for forming a resist pattern on the substrate, and a method of manufacturing a conductor pattern, a printed wiring board, a lead frame, a substrate, and a semiconductor package using the photosensitive resin laminate.

The above object can be attained by the following configuration of the present invention. That is, this invention is as follows.

[1] A thermoplastic resin having an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000 polymerized using the following (a) to (d) components and (a) at least an α, β-unsaturated carboxyl group-containing monomer as a polymerization component. 20 to 90 mass% of polymer, (b) 3 to 75 mass% of addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule, (c) 0.01 to 30 mass% of photopolymerization initiator, and (d) General formula (Ⅰ):

[Formula 1]

(Wherein, R ₁ to R ₅ are each independently H, an aryl group or an arylalkyl group, and at least one of R ₁ to R ₅ is an aryl group or an arylalkyl group, and A ¹ is C ₂ H ₄ or C ₃ H ₆ a, n a plurality of a ¹ are be the same or different from each other even if at least _one is 2, and n ₁ is an integer of 1 to 50)

Photosensitive resin composition containing the compound shown by.

[2] The photosensitive resin composition according to the above [1], wherein at least one of R ₁ to R ₅ in General Formula (I) is a phenylalkyl group.

[3] The photosensitive resin composition according to the above [2], wherein the alkyl group moiety in the phenylalkyl group is 1 to 6 carbon atoms.

[4] The photosensitive resin composition according to any one of [1] to [3], wherein one to three groups in R ₁ to R ₅ in General Formula (I) are each an aryl group or an arylalkyl group.

[5] The photosensitive resin composition according to any one of the above [1] to [3], wherein two or three groups in R ₁ to R ₅ in General Formula (I) are each an aryl group or an arylalkyl group.

[6] The photosensitive resin composition according to any one of the above [1] to [5], wherein n ₁ is an integer of 1 to 35 in the general formula (I).

[7] R ₁ to R ₅ in General Formula (I) are each independently H, a phenyl group or a 1-phenylethyl group, two of R ₁ to R ₅ are H, and three of R ₁ to R ₅ are each The photosensitive resin composition in any one of said [1]-[6] which is independently a phenyl group or 1-phenylethyl group.

[8] The content of any of the above [1] to [7], wherein the content of the component (d) when the total amount of the components (a), (b) and (c) is 100 mass% is 1 to 20 mass%; The photosensitive resin composition of one.

[9] As the component (b), the following general formula (II):

[Formula 2]

(Wherein R ₆ and R ₇ are each independently H or CH ₃ , and n ₂ , n ₃ and n ₄ are each independently an integer of 3 to 20) or the following general formula (III):

(3)

(Wherein R ₈ and R ₉ are each independently H or CH ₃ , A ² is C ₂ H ₄ , A ³ is C ₃ H ₆ , and n ₅ and n ₆ are each independently 1-29 Is an integer, n ₅ + n ₆ is an integer of 2 to 30, n ₇ and n ₈ are each independently an integer of 0 to 29, and n ₇ + n ₈ is an integer of 0 to 30,-(A ² -O) The arrangement of the repeating units of-and-(A ³ -O)-may be random or a block, and in the case of a block, any of-(A ² -O)-and-(A ³ -O)-is a bisphenyl group side The photosensitive resin composition in any one of said [1]-[8] containing the unsaturated compound which can be superposed | polymerized as represented by the above).

[10] A photosensitive resin laminate obtained by laminating the photosensitive resin composition according to any one of the above [1] to [9] on a support.

[11] A lamination step of forming the photosensitive resin laminate according to the above [10] on a substrate, an exposure step of exposing the photosensitive resin laminate, and an unexposed portion of the photosensitive resin in the photosensitive resin laminate A resist pattern forming method comprising a developing step of forming a resist pattern.

[12] A lamination step of forming the photosensitive resin laminate according to the above [10] on a substrate which is a metal plate or a metal film insulating plate, an exposure step of exposing the photosensitive resin laminate, and a photosensitive resin in the photosensitive resin laminate. And a developing step of forming a resist pattern by removing the unexposed portions of the film, and forming a conductor pattern by etching or plating the substrate on which the resist pattern is formed.

[13] A lamination step of forming the photosensitive resin laminate according to the above [10] on a substrate which is a copper clad laminate or a flexible substrate, an exposure step of exposing the photosensitive resin laminate, and a photosensitive resin in the photosensitive resin laminate. The manufacturing method of the printed wiring board containing the image development process of removing the unexposed part of this, and forming a resist pattern, the process of etching or plating the board | substrate with which the resist pattern was formed, and the process of peeling the resist pattern from this board | substrate.

[14] A lamination step of forming the photosensitive resin laminate according to the above [10] on a substrate which is a metal plate, an exposure step of exposing the photosensitive resin laminate, and an unexposed portion of the photosensitive resin in the photosensitive resin laminate. And a step of etching the substrate on which the resist pattern is formed, and a step of peeling the resist pattern from the substrate.

[15] A lamination step of forming a photosensitive resin laminate according to the above [10] on a substrate which is a glass substrate coated with a glass rib paste, an exposure step of exposing the photosensitive resin laminate, and the photosensitive resin laminate. And a concave-convex pattern comprising a developing step of removing an unexposed portion of the photosensitive resin to form a resist pattern, a step of sandblasting the substrate on which the resist pattern is formed, and a step of peeling the resist pattern from the substrate. The manufacturing method of a base material.

[16] A lamination step of forming the photosensitive resin laminate according to the above [10] on a substrate which is a wafer on which circuit formation as LSI is completed, an exposure step of exposing the photosensitive resin laminate to the photosensitive resin laminate, A method of manufacturing a semiconductor package comprising a developing step of removing an unexposed portion of the photosensitive resin to form a resist pattern, plating the substrate on which the resist pattern is formed, and peeling the resist pattern from the substrate.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which is excellent in the resolution, adhesiveness, and tentability, and has the outstanding peelability by the aqueous alkali solution of a cured resist film, the photosensitive resin laminated body using this photosensitive resin composition, and the fixed using the photosensitive resin laminated body A method for forming three resist patterns can be provided. Moreover, using the photosensitive resin laminated body, it becomes possible to manufacture a high definition printed wiring board, a lead frame, a semiconductor package, and also a flat panel display.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely.

<Photosensitive resin composition>

The photosensitive resin composition of this invention has the acid equivalent of 100-600, and the weight average molecular weight polymerized using the following (a)-(d) component and (a) at least the (alpha), (beta)-unsaturated carboxyl group-containing monomer as a polymerization component. 20 to 90% by mass of a thermoplastic polymer of 5,000 to 500,000 (hereinafter also referred to as (a) thermoplastic polymer), (b) an addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule (hereinafter, (b) addition 3 to 75 mass% (also referred to as polymerizable monomer), (c) photopolymerization initiator (hereinafter also referred to as (c) photopolymerization initiator) 0.01 to 30 mass%, and (d) the following general formula (I):

[Formula 4]

(Wherein, R ₁ to R ₅ are each independently H, an aryl group or an arylalkyl group, and at least one of R ₁ to R ₅ is an aryl group or an arylalkyl group, and A ¹ is C ₂ H ₄ or C ₃ H ₆ and, n ₁ is 2, a plurality of a ¹ may be the same and will be different, or more, and n ₁ is represented by the compound (or less, (d) general formula (ⅰ) represented by an integer from 1 to 50) Also referred to as a compound).

(a) thermoplastic polymer

The (a) thermoplastic polymer is a thermoplastic polymer having at least an α, β-unsaturated carboxyl group-containing monomer as a polymerization component, an acid equivalent of 100 to 600, and a weight average molecular weight of 5,000 to 500,000.

The carboxyl group in the (a) thermoplastic polymer is necessary for the photosensitive resin composition of the present invention to have developability or peelability with respect to a developing solution or a peeling solution composed of an aqueous alkali solution. (a) The acid equivalent of a thermoplastic polymer is 100-600, Preferably it is 250-450. An acid equivalent is 100 or more from a viewpoint of ensuring compatibility with the other component in a solvent or the photosensitive resin composition, especially (b) addition polymerizable monomer mentioned later, and 600 or less from a viewpoint of maintaining developability and peelability. . Here, an acid equivalent refers to the mass (gram) of the thermoplastic polymer which has a 1 equivalent carboxyl group in it. In addition, the measurement of an acid equivalent is performed by potentiometric titration with 0.1 mol / L NaOH aqueous solution using the hiranuma reporting titrator (COM-555), for example.

The weight average molecular weight of (a) thermoplastic polymer is 5,000-500,000. A weight average molecular weight is 5,000 or more from a viewpoint of maintaining the thickness of the photosensitive resin laminated body (namely, dry film resist) uniformly, and obtaining tolerance to a developing solution, and 500,000 or less from a viewpoint of maintaining developability. Preferably the weight average molecular weight is 20,000-100,000. The weight average molecular weight in this specification means the weight average molecular weight measured using the calibration curve of polystyrene (for example, Shodex STANDARD SM-105 by Showa Denko) by gel permeation chromatography (GPC). do. The weight average molecular weight can be measured on condition of the following using Nippon spectroscopy Co., Ltd. gel permeation chromatography.

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 kind of polymer or two or more kinds of copolymers of the first monomer described later, or one kind of polymer or two or more kinds of air, described later, from the viewpoint of image formation after alkali development. It is preferable that it is a copolymer or 1 or more types of copolymers of the 1st monomer of this 1st monomer and this 2nd monomer.

The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. As a 1st monomer, (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid semiester are mentioned, for example. Especially, (meth) acrylic acid is preferable from a developable viewpoint by alkaline solution. Here, (meth) acryl represents acryl or methacryl. It is the same below.

The second monomer is non-acidic and is a monomer having at least one polymerizable unsaturated group in the molecule. As a 2nd monomer, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, for example. , iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2 Ester of vinyl alcohol, such as ethylhexyl (meth) acrylate, benzyl (meth) acrylate, and vinyl acetate, (meth) acrylonitrile, styrene, and the styrene derivative which can superpose | polymerize are mentioned. Especially, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are especially preferable from an image forming viewpoint.

(a) More specific examples of the thermoplastic polymer include polymers containing methyl methacrylate, methacrylic acid and styrene as copolymerization components, polymers containing methyl methacrylate, methacrylic acid and n-butyl acrylate as copolymerization components, And polymers containing benzyl methacrylate, methyl methacrylate and 2-ethylhexyl acrylate as copolymerization components.

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

(b) addition polymerizable monomers

(b) The addition polymerizable monomer has at least one polymerizable ethylenically unsaturated bond in the molecule. It is preferable that an ethylenically unsaturated bond is a terminal ethylenically unsaturated group from a viewpoint of image formation property favorable. From the viewpoint of high resolution and edge fuse suppression, it is preferable to contain at least one unsaturated polymerizable photopolymerizable compound represented by the following general formula (II) or (III) as the (b) addition polymerizable monomer.

[Chemical Formula 5]

(Wherein R ₆ and R ₇ are each independently H or CH ₃ , and n ₂ , n ₃ and n ₄ are each independently an integer of 3 to 20)

[Formula 6]

(Wherein R ₈ and R ₉ are each independently H or CH ₃ , A ² is C ₂ H ₄ , A ³ is C ₃ H ₆ , and n ₅ and n ₆ are each independently 1-29 Is an integer and n ₅ + n ₆ is An integer of 2 to 30, n ₇ and n ₈ are each independently an integer of 0 to 29, and n ₇ + n ₈ is an integer of 0 to 30,-(A ² -O)-and-(A ³ -O The array of repeating units of)-may be random or a block, and in the case of a block, any of-(A ² -O)-and-(A ³ -O) may be a bisphenyl group side)

In the compound represented by the said general formula (II), n <_2> , n <_3> and n <_4> are respectively 3 or more and 20 or less independently. n <_2> , n <_3> and n <_4> are three or more in the point which a tentability improves, and are 20 or less in the point which improves a sensitivity and a resolution. More preferably n ₂ and n ₄ Are each independently 3 or more and 10 or less, and n ₃ This is 5 or more and 15 or less.

In the compound represented by the general formula (III), n ₅ and n ₆ are each independently an integer of 1 to 29, and n ₅ + n ₆ is It is an integer of 2-30. n ₅ and n ₆ is 1 or greater in the cured resist film flexibility point of view, is 29 or less from the viewpoint that a sufficient sensitivity is obtained. n <_5> + n <_6> is two or more from a viewpoint of tentability, and is 30 or less from a viewpoint of image formation. In addition, in the compound represented by the general formula (III), n ₇ and n ₈ are each independently an integer of 0 to 29, and n ₇ + n ₈ is an integer of 0 to 30. n ₇ and n ₈ is 29 or less from the viewpoint that a sufficient sensitivity is obtained. n <_7> + n <_8> is 30 or less from a developer cohesion viewpoint.

In the compound represented by the general formula _{(Ⅲ), n 5 + n} 6 + n ₇ + n ₈ are values of 2 or higher is preferred, and also preferably not more than 40. From the viewpoint of flexibility and tentability of the cured resist film obtained by curing the photosensitive resin composition, the value is preferably 2 or more, and the value is preferably 40 or less from the effect on the resolution. As a specific example of the unsaturated compound represented by the said General formula (III), the dimethacrylate of polyethyleneglycol which added an average of 2 mol ethylene oxide to both ends of bisphenol A (for example, Shin-Nakamura Chemical Industry Co., Ltd. product) NK ester BPE-200) and dimethacrylate of polyethyleneglycol which added an average of 5 mol of ethylene oxide to both ends of bisphenol A (for example, NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.) and bisphenol A Dimethacrylate of polyalkylene glycol added with an average of 6 moles of ethylene oxide and an average of 2 moles of propylene oxide at each end of, and 15 moles of ethylene oxide and an average of 2 moles of propylene oxide at both ends of bisphenol A. Dimethacrylate of the polyalkylene glycol added, etc. are mentioned.

(b) The ratio of the photopolymerizable unsaturated compound represented by the general formula (II) in the addition polymerizable monomer is preferably 3% by mass or more in terms of improving the sensitivity, resolution, adhesiveness and tentability, and the edge fuse 70 mass% or less is preferable at the point which is suppressed. More preferably, the said ratio is 3 mass% or more and 50 mass% or less, More preferably, it is 3 mass% or more and 30 mass% or less.

(b) The ratio of the photopolymerizable unsaturated compound represented by the general formula (III) in the addition polymerizable monomer is preferably 3% by mass or more from the viewpoint of improving the sensitivity, and 70% by mass from the viewpoint of suppressing the edge fuse. The following is preferable. More preferably, the said ratio is 10-65 mass%, More preferably, it is 15-55 mass%.

As the (b) addition polymerizable monomer used in the photosensitive resin composition of the present invention, in addition to the compounds represented by the general formulas (II) and (III), a known compound having at least one polymerizable ethylenically unsaturated bond can be used. Can be. As such a compound, for example, 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate, 2-hydroxy-3- phenoxypropyl acrylate, phenoxy hexaethylene glycol acrylate, phthalic anhydride and 2-hydroxy A reaction product of a half ester compound with oxypropyl acrylate and a propylene oxide (e.g., Nippon Catalyst Chemical Co., OE-A 200), 4-normaloctylphenoxypentapropylene glycol acrylate, 1,6-hexanediol ( Polyoxyalkylene glycol di (meth), such as a meth) acrylate, 1, 4- cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate Acrylate, 2-di (p-hydroxyphenyl) propanedi (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol penta (meth) acrylate, trimethylolprop It contains urethane groups, such as a triglycidyl ether tri (meth) acrylate, 2, 2-bis (4-methacryloxy pentaethoxyphenyl) propane, and a urethane compound of hexamethylene diisocyanate and nonapropylene glycol monomethacrylate. The polyfunctional (meth) acrylate which is mentioned, and the polyfunctional (meth) acrylate of the isocyanuric acid ester compound are mentioned. These may be used independently and may use two or more types together.

The amount of the (b) addition polymerizable monomer in the photosensitive resin composition of this invention is the range of 3-75 mass%, and a more preferable range is 15-70 mass%. This amount is 3 mass% or more from the viewpoint of suppressing the curing failure of the photosensitive resin composition and the delay of the developing time, and is 75 mass% or less from the viewpoint of suppressing the delay of peeling of the cold flow and the cured resist.

(c) photoinitiator

(c) As a photoinitiator, what is normally used as a photoinitiator of photosensitive resin can be used suitably, Especially hexaaryl bisimidazole (henceforth triaryl imidazolyl dimer) is used preferably. As a triaryl imidazolyl dimer, it is a 2- (o-chlorophenyl) -4,5-diphenyl imidazolyl dimer (hereafter, 2,2'-bis (2-chlorophenyl)-). Also known as 4,4 ', 5,5'-tetraphenyl-1,1'-bisimidazole), 2,2', 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxy Phenyl) -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) -imida Zolyl 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-difluoro Rophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxy Nil) -imidazolyl dimer, 2,2'-bis- (2,6-difluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imida Zolyl dimer, 2,2'-bis- (2,3,4-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer , 2,2'-bis- (2,3,5-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2, 2'-bis- (2,3,6-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 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 preferably used as a photoinitiator having a high effect on resolution and strength of the cured resist film. These may be individual or may be used in combination of 2 or more types.

(c) It is preferable to contain an acridine compound and / or a pyrazoline compound as a photoinitiator from a viewpoint that photocuring advances with favorable sensitivity. Examples of the acridine compound include acridine, 9-phenylacridine, 9- (4-tolyl) acridine, 9- (4-methoxyphenyl) acridine, and 9- (4-hydroxyphenyl ) Acridine, 9-ethylacridine, 9-chloroethylacridine, 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-bromophenyl) 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. Among them, 9-phenylacridine is preferable from the viewpoint of image formation.

Moreover, as a pyrazoline compound, 1-phenyl- 3- (4-tert- butyl- styryl) -5- (4-tert- butyl- phenyl) -pyrazoline from a viewpoint of photocuring with favorable sensitivity, 1 -(4- (benzooxazol-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 and the like This is preferred.

Moreover, as a photoinitiator of that excepting the above, 2-ethyl anthraquinone, an octaethyl anthraquinone, a 1, 2- benzanthhraquinone, a 2, 3- benzanthhraquinone, 2-phenyl anthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and Quinones such as 3-chloro-2-methylanthraquinone, benzophenone, Michler's ketone [4,4'-bis (dimethylamino) benzophenone], and 4,4'-bis (diethylamino) benzophenone Of benzoin ethers such as aromatic ketones, benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin, benzyl dimethyl ketal, benzyl diethyl ketal, thioxanthones and alkylaminobenzoic acid Combinations and oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzoinoxime and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime Can be mentioned. Moreover, as a combination of the thioxanthones and alkylamino benzoic acid which were mentioned above, the combination of ethyl thioxanthone and ethyl dimethyl amino benzoate, the combination of 2-chloro thioxanthone and ethyl dimethyl amino benzoate, and isopropyl, for example And combinations of thioxanthone and ethyl dimethylaminobenzoate. Moreover, you may use N-arylamino acid. Examples of N-arylamino acids include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. Especially, N-phenylglycine is especially preferable from a viewpoint of a sensitivity increase.

The amount of (c) photoinitiator in the photosensitive resin composition is the range of 0.01-30 mass%, and a preferable range is 0.05-10 mass%. The above amount is 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity at the time of photopolymerization by exposure, and at the time of photopolymerization, the light is sufficiently transmitted to the bottom of the photosensitive resin composition (i.e., a part far from the light source), thereby achieving good resolution. It is 30 mass% or less from a viewpoint of obtaining a property and adhesiveness.

(d) Compound represented by general formula (I)

The photosensitive resin composition of this invention, (d) General formula (I):

[Formula 7]

(Wherein, R ₁ to R ₅ are each independently H, an aryl group or an arylalkyl group, and at least one of R ₁ to R ₅ is an aryl group or an arylalkyl group, and A ¹ is C ₂ H ₄ or C ₃ H ₆ a, n a plurality of a ¹ are may be the same with each other or different, and n ₁ is an image formed by one or not less than 50 kinds of the compounds represented by the integer a) one or two of not less than _1, the second resistance and It has the advantage of maintaining tentability and shortening the peeling time of the photocured film by aqueous alkali solution.

In General Formula (I), R <_1> -R <_5> is respectively independently H, an aryl group, or an arylalkyl group. In the present specification, the arylalkyl group is one in which the hydrogen 1 atom of the alkyl group is substituted with an aryl group. An aryl group is a general term of the residue remove | excluding one hydrogen atom from the nucleus of an aromatic hydrocarbon, A substituted or unsubstituted phenyl group, tolyl group, xylyl group, naphthyl group, mesityl group, etc. are mentioned. Examples of the arylalkyl group include a phenylalkyl group such as a benzyl group and a phenylethyl group, cumyl group, and the like. A phenylalkyl group is preferable from the viewpoint of good adhesion, and a phenylethyl group is more preferable.

At least 1 of R <_1> -R <_5> is an aryl group or an arylalkyl group. As a result, good adhesion is obtained. Moreover, when 1-3, especially 2 or 3 of R <_1> -R <_5> are an aryl group or an arylalkyl group, it is preferable at the point that resolution and adhesiveness become favorable.

Moreover, it is especially preferable that at least 1 of R <_1> -R <_5> is a phenylalkyl group.

R ₁ to R ₅ are each independently H, a phenyl group, or 1-phenylethyl group, two of R ₁ to R ₅ are H, and three of R ₁ to R ₅ are each independently a phenyl group or 1-phenylethyl group. the combination of the R ₁ ~ R ₅ is preferable in terms that reduce the separation time. In addition, the aspect of the combination of that excepting the above of R <_1> -R <_5> , ie, R <_1> -R <_5> is respectively independently H, an aryl group, or an arylalkyl group, and at least 1 of R <_1> -R <_5> is an aryl group or an arylalkyl group Although a combination of, R ₁ ~ R ₅ is, R ₁ ~ R ₅ and the two are also aspects of the H to the condition that three of the R ₁ ~ R ₅ are each independently other than a phenyl or 1-phenylethyl group is in the combination, Development cohesion is preferable from a good viewpoint.

It is preferable that the arylalkyl group has 1 to 6 carbon atoms in the alkyl group moiety, and when the carbon number is in this range, the cohesiveness is better. More preferably, the said carbon number is 1-3 pieces.

A ¹ in the general formula (Ⅰ) is C ₂ H ₄ or C ₃ H _6, whereby the advantage of the good cohesiveness after development can be obtained.

The repeating number n ₁ of the repeating unit-(A ¹ -O)-in General Formula (I) is 1 to 50, and when n ₁ is 2 or more, a plurality of A ¹ may be the same as or different from each other. n ₁ is 1 or more in terms satisfactorily obtain a coherent, is 50 or less in terms satisfactorily obtain the image-forming properties and adhesion. In view adhesion becomes more favorable, n ₁ is preferably an integer of 1-35. The repeating unit-(A ¹ -O)-can also be repeated randomly or in blocks.

Content of the compound represented by (d) General formula (I) in the photosensitive resin composition is a thing of 1-20 mass%, when the total amount of the said (a), (b) and (c) component is 100 mass%. Preferably, it is the range of 2-10 mass% more preferably. When the said content is 1 mass% or more, cohesiveness after image development of the photosensitive resin composition becomes favorable, and when it is 20 mass% or less, developability and image formation property are favorable.

(d) As a compound represented by general formula (I), what is commercially available is, for example, New Cole 610 (made by Nippon Emulsifier Co., Ltd.), New call 610 (80) (made by Nippon Emulsifier Co., Ltd.), New call 2604 (Nippon Emulsifier Co., Ltd.). New Kohl 2607 (manufactured by Nippon Emulsifier Co., Ltd.), New Kohl 2609 (manufactured by Nippon Emulsifier Co., Ltd.), New Kohl 2614 (manufactured by Nippon Emulsifier Co., Ltd.), New Kohl 707-F (manufactured by Nippon Emulsifier Co., Ltd.), New Kohl 710-F (manufactured by Nippon Emulsifier Co., Ltd.) ), Newcall 714-F (manufactured by Nippon Emulsifier Co., Ltd.), Newcall 2608-F (manufactured by Nippon Emulsifier Co., Ltd.), Newcall 2600-FB (manufactured by Nippon Emulsifier Co., Ltd.), Newcall 2616-F (manufactured by Nippon Emulsifier Co., Ltd.), Newcall 3612-FA (Nippon Emulsifier Co., Ltd.) etc. are mentioned, Especially, from the viewpoint of shortening peeling time efficiently, More preferably, Nucol 2604 (made by Nippon Emulsifier Co., Ltd.), Nucol 26 07 (manufactured by Nippon Emulsifier Co., Ltd.), Nucol 2609 (manufactured by Nippon Emulsifier Co., Ltd.) and Nucoll 2614 (manufactured by Nippon Emulsifier Co., Ltd.).

The photosensitive resin composition of this invention can be made to contain various additives as another component of the said (a)-(d) component. Specifically, coloring substances, such as dye and a pigment, can be employ | adopted, for example. As such a coloring substance, phthalocyanine green, crystal violet, methyl orange, nile blue 2B, Victoria blue, malachite green, basic blue 20, diamond green, etc. are mentioned, for example.

Moreover, you may contain a coloring agent in the photosensitive resin composition so that a visual image may be provided by exposure. As such a coloring agent, dye, such as a leuco dye or the combination of a fluorane dye and a halogen compound, is mentioned. As the halogen compound, amyl bromide, isoamyl bromide, isobutyl bromide, ethylene bromide, diphenyl methyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2,3-dibro) Mopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, chlortritriazine compounds and the like Can be mentioned.

As for content of the coloring substance and color development agent in the photosensitive resin composition, respectively, 0.01-10 mass% is preferable. 0.01 mass% or more is preferable at the point from which the favorable coloring property and color development property are acquired, and 10 mass% or less is preferable at the point where the contrast of an exposed part and an unexposed part is favorable, and the storage stability is favorable.

Moreover, in order to improve the thermal stability and the storage stability of the photosensitive resin composition, it is preferable to contain at least 1 type of compound chosen from the group which consists of a radical polymerization inhibitor, benzotriazoles, and carboxy benzotriazoles in a photosensitive resin composition. .

As the radical polymerization inhibitor, for example, 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 diphenylnitrosoamine.

Moreover, as benzotriazole, 1, 2-, 3- benzotriazole, 1-chloro- 1, 2, 3- benzotriazole, bis (N-2-ethylhexyl) amino methylene- 1, 2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, and bis (N-2-hydroxyethyl) aminomethylene-1,2,3- Benzotriazole is mentioned.

Moreover, as carboxy benzotriazoles, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N- (N, N-di-, for example) 2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) amino Ethylene carboxy benzotriazole is mentioned.

Preferably the sum total content of the radical polymerization inhibitor, benzotriazoles, and carboxy benzotriazoles in the photosensitive resin composition is 0.01-3 mass%, More preferably, it is 0.05-1 mass%. 0.01 mass% or more is preferable from a viewpoint of providing the storage composition with favorable storage stability, and 3 mass% or less is preferable from a viewpoint of maintaining favorable exposure sensitivity.

You may contain a plasticizer in the photosensitive resin composition as needed. As a plasticizer, for example, polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene Glycol esters such as monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, phthalic acid esters such as diethyl phthalate, o-toluene sulfonic acid amide, p-toluene sulfonic acid amide, and citric acid tree Butyl, triethyl citrate, acetyl triethyl citrate, acetyl citrate tri-n-propyl, acetyl citrate tri-n-butyl 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 flexibility to a cured resist film, and 50 mass% or less is preferable from a viewpoint of suppressing hardening shortage or cold flow.

<Photosensitive resin composition preparation liquid>

The photosensitive resin composition of this invention can be used for various uses also as a photosensitive resin composition preparation liquid formed by adding a solvent to the photosensitive resin composition. As a preferable solvent, ketones represented by methyl ethyl ketone (MEK) and alcohols, such as methanol, ethanol, and isopropyl alcohol, are mentioned. It is preferable to adjust the quantity of the solvent added to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid may be 500-4000 mPa * sec at 25 degreeC.

<Photosensitive resin laminated body>

This invention also provides the photosensitive resin laminated body formed by laminating | stacking the photosensitive resin composition of this invention as mentioned above on a support body. The photosensitive resin laminated body may have a protective layer on the surface on the opposite side to the support body side of the layer (henceforth a photosensitive resin layer) which consists of a photosensitive resin composition.

As a support body, the transparent thing which permeate | transmits the light radiated | emitted from an exposure light source is preferable. As such a support body, a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, a polystyrene film , Polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film and the like. As these films, what was extended as needed can be used. The haze of the support is preferably 5 or less. Although the thickness of the support is advantageous in terms of image formation and economical efficiency, it is preferably used in the range of 10 to 30 µm for the necessity of maintaining the strength.

In the case of forming a protective layer in the photosensitive resin laminate, an important characteristic of the protective layer is that the adhesion between the photosensitive resin layer and the protective layer is sufficiently small as compared with the adhesion between the photosensitive resin layer and the support, and the protective layer is a photosensitive resin layer. It can be easily peeled from. For example, a polyethylene film, a polypropylene film, or the like can be preferably used as the protective layer. Moreover, the film excellent in the peelability disclosed in Unexamined-Japanese-Patent No. 59-202457 can be used preferably. 10-100 micrometers is preferable and, as for the film thickness of a protective layer, 10-50 micrometers is more preferable.

The thickness of the photosensitive resin layer in the photosensitive resin laminated body becomes like this. Preferably it is 5-100 micrometers, More preferably, it is 7-60 micrometers. The thinner the thickness, the higher the resolution, and the thicker the film, the higher the film strength. Therefore, the thickness can be appropriately selected depending on the application.

A method known in the art can be adopted as a method of sequentially laminating a support, a photosensitive resin layer, and a protective layer as necessary to produce the photosensitive resin laminate of the present invention.

For example, using the photosensitive resin composition of this invention used for the photosensitive resin layer, the above-mentioned photosensitive resin composition preparation liquid is prepared, This is first apply | coated on a support body using a bar coater or a roll coater, and it is made to dry, The photosensitive resin layer which consists of this photosensitive resin composition is laminated | stacked on it. Next, a protective layer is laminated on the photosensitive resin layer as needed. The photosensitive resin laminated body can be produced by the above.

<Resist Pattern Forming Method>

This invention also provides the resist pattern formation method using the photosensitive resin laminated body of this invention mentioned above. The resist pattern forming method includes a lamination step of forming a photosensitive resin laminate on a substrate, an exposure step of exposing the photosensitive resin laminate, and an unexposed portion of the photosensitive resin in the photosensitive resin laminate to remove the resist. And a developing step of forming a pattern. Specific examples of the resist formation method will be described below.

First, a lamination process is performed using a laminator. When the photosensitive resin laminated body has a protective layer, after peeling a protective layer, a photosensitive resin layer is heat-compression-bonded to a board | substrate surface with a laminator and it laminates. In this case, the photosensitive resin layer may be laminated only on one side of the substrate surface, or may be laminated on both sides as necessary. The heating temperature at this time is generally 40-160 degreeC. Moreover, when performing the heat press bonding twice or more, the adhesiveness with respect to the board | substrate of the resist pattern obtained improves. At this time, crimping | bonding may be performed using the two-stage laminator provided with the double roll, and the photosensitive resin layer may be crimped | bonded to the board | substrate surface by passing a photosensitive resin laminated body and a board | substrate several times repeatedly through a roll.

Next, an exposure process is performed using an exposure machine. After peeling a support body as needed, it passes through a photomask and exposes to the photosensitive resin layer with actinic light. The exposure amount is determined in accordance with the light source illuminance and the exposure time. You may measure an exposure amount using a photometer.

In an exposure process, you may use the maskless exposure method. In maskless exposure, it does not use a photomask but exposes directly on a board | substrate by the drawing apparatus. 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 in accordance with the illuminance of the exposure light source and the moving speed of the substrate.

Next, a developing process is performed using a developing apparatus. After exposure, when a support body exists on the photosensitive resin layer, this is removed. Then, the unexposed part of photosensitive resin is image-developed and removed using the developing solution which consists of aqueous alkali solution, and a resist pattern is obtained. With an aqueous alkali solution is an aqueous solution, such as Na ₂ CO _3, or K ₂ CO ₃ are preferred. These are selected according to the characteristics of the photosensitive resin layer, but an aqueous solution of Na ₂ CO _{3 at a} concentration of 0.2 to 2% by mass is common. In the aqueous alkali solution, a small amount of an organic solvent for promoting the development of a surface active agent, an antifoaming agent, and the like may be mixed. In addition, it is preferable to maintain the temperature of the developing solution in a developing process at a fixed temperature in the range of 20-40 degreeC.

Although a resist pattern is obtained by the above-mentioned process, in some cases, the heating process of 100-300 degreeC can also be performed further. By performing this heating process, further chemical-resistant improvement is attained. For the heating, a heating furnace such as hot air, infrared rays, or far infrared rays can be used.

<Manufacturing method of a conductor pattern, manufacturing method of a printed wiring board>

This invention also provides the method of manufacturing a conductor pattern using the photosensitive resin laminated body mentioned above, and the method of manufacturing a printed wiring board using the photosensitive resin laminated body mentioned above. The manufacturing method of a conductor pattern is the lamination process of forming the photosensitive resin laminated body of this invention mentioned above on the board | substrate which is a metal plate or a metal film insulation board, for example, a copper clad laminated board, the exposure process which exposes the photosensitive resin laminated body, and photosensitive The development process of removing the unexposed part of the photosensitive resin in a resin laminated body, and forming a resist pattern, and etching or plating the board | substrate with which the resist pattern was formed (for example, the copper surface of a board | substrate in a copper clad laminated board). It includes the step of forming a conductor pattern. In a lamination process, an exposure process, and a developing process, the method and conditions similar to the above-mentioned in the resist pattern formation method can be employ | adopted preferably.

Moreover, the manufacturing method of a printed wiring board is the lamination process of forming the photosensitive resin laminated body of this invention mentioned above on the board | substrate which is a copper clad laminated board or a flexible substrate, the exposure process which exposes to the photosensitive resin laminated body, and the photosensitive resin laminated body. The developing process of removing the unexposed part of the photosensitive resin in this case, and forming a resist pattern, the process of etching or plating the board | substrate with a resist pattern, and the process of peeling a resist pattern from a board | substrate. Typically, after performing the lamination process, the exposure process and the developing process in the same method and conditions as described above in the resist pattern forming method, the exposed substrate is treated by a known method such as an etching method or a plating method, Moreover, a desired printed wiring board can be obtained by performing the peeling process of peeling a resist pattern from a board | substrate with the aqueous solution which has stronger alkalinity than a developing solution. Although there is no restriction | limiting in particular also about the aqueous alkali solution for peeling (henceforth "a peeling liquid"), The aqueous solution of NaOH or KOH of 2-5 mass% concentration is generally used. It is possible to add a small amount of water-soluble solvent to the stripping solution. Moreover, it is preferable that the temperature of the peeling liquid in a peeling process is the range of 40-70 degreeC.

<Production method of the lead frame>

This invention also provides the method of manufacturing a lead frame using the photosensitive resin laminated body of this invention mentioned above. The method includes a lamination step of forming the photosensitive resin laminate of the present invention described above on a substrate which is a metal plate, an exposure step of exposing the photosensitive resin laminate, and an unexposed portion of the photosensitive resin in the photosensitive resin laminate. A developing step of removing and forming a resist pattern, a step of etching a substrate on which a resist pattern is formed, and a step of peeling a resist pattern from the substrate. Typically, using a metal plate such as copper, a copper alloy, or an iron-based alloy as a substrate, the lamination step, the exposure step, and the developing step are performed after the same method and conditions as described above in the resist pattern forming method, followed by exposure. The board | substrate is etched and the conductor pattern is formed. Then, the peeling process of peeling a resist pattern by the method similar to the manufacturing method of the printed wiring board mentioned above can be performed, and a desired lead frame can be obtained.

<The manufacturing method of the base material which has an uneven pattern>

This invention also provides the method of manufacturing the base material which has an uneven | corrugated pattern using the photosensitive resin laminated body mentioned above. The method includes a lamination step of forming a photosensitive resin laminate on a substrate which is a glass substrate coated with glass rib paste, an exposure step of exposing the photosensitive resin laminate, and an unexposed portion of the photosensitive resin in the photosensitive resin laminate. And a process of sandblasting the substrate on which the resist pattern is formed, and a process of peeling the resist pattern from the substrate. In a lamination process, an exposure process, and a developing process, the method and conditions similar to the above-mentioned in the resist pattern formation method can be employ | adopted preferably. The resist pattern formed in the manufacturing method of the base material can be used as a protective mask member at the time of processing a board | substrate by a sandblasting method.

Moreover, you may use board | substrates, such as glass, a silicon wafer, amorphous silicon, polycrystalline silicon, a ceramic, sapphire, and a metal material, in addition to the glass substrate which apply | coated the glass rib paste mentioned above. Typically, a lamination process, an exposure process, and a development process are performed on the board | substrate which apply | coated the glass rib paste by the method similar to the resist pattern formation method mentioned above, and a resist pattern is formed. Thereafter, the substrate is subjected to a sand blast treatment step of spraying a blast material from the formed resist pattern and cutting it to a desired depth, and a peeling step of removing the resist pattern portion remaining on the substrate from the substrate with an alkali stripper or the like. The base material which has a fine uneven | corrugated pattern in can be formed. Blasting a material used in the sandblasting treatment process is known to be used, for example, SiC, SiO _2, Al ₂ O _3, CaCO _3, ZrO, particle size 2 to fine particles are used of approximately 100 ㎛ of glass, stainless steel, etc. do.

<Method of Manufacturing Semiconductor Package>

This invention also provides the method of manufacturing a semiconductor package using the photosensitive resin laminated body mentioned above. The method includes a lamination step of forming the photosensitive resin laminate of the present invention described above on a substrate which is a wafer having completed circuit formation as LSI, an exposure step of exposing the photosensitive resin laminate, and the photosensitive resin in the photosensitive resin laminate. The developing process of removing the unexposed part of resin and forming a resist pattern, the process of plating the board | substrate with a resist pattern, and the process of peeling a resist pattern from a board | substrate. Typically, in the resist pattern forming method, after performing the lamination process, the exposure process, and the developing process under the same method and conditions as described above, the exposed openings are subjected to columnar plating such as copper and solder to form a conductor pattern. Carry out the process. Then, the desired semiconductor package is implemented by performing a peeling process of peeling a resist pattern by the same method as the manufacturing method of the above-mentioned printed wiring board, and also removing the thin metal layer of parts other than columnar plating by etching. Can be obtained.

Example

Hereinafter, although an Example further demonstrates this invention, this invention is not limited to this. The preparation method of the sample for evaluation of an Example and a comparative example, the evaluation method, and the evaluation result about the obtained sample are demonstrated below.

(Examples 1-13, Comparative Examples 1 and 2)

The compound shown in Table 1 was mixed by the mass part shown in Table 2 and 3, and the photosensitive resin composition was obtained. In Tables 2 and 3, MEK represents methyl ethyl ketone, and the mass part in the composition ratio of compounds other than MEK is a value including MEK.

1. Preparation of Samples for Evaluation

The photosensitive resin laminated body in an Example and a comparative example was produced as follows.

<Production of Photosensitive Resin Laminate>

The photosensitive resin composition of each Example and each comparative example was stirred and mixed well, and each composition was apply | coated uniformly using the bar coater to the polyethylene terephthalate film surface of thickness of 16 micrometers as a support body, It dried for minutes, and formed the photosensitive resin layer. The thickness of the photosensitive resin layer was 40 micrometers.

Subsequently, a 22 micrometer-thick polyethylene film was adhered as a protective layer on the surface in which the polyethylene terephthalate film of the photosensitive resin layer was not laminated, and the photosensitive resin laminated body was obtained.

<The board front>

As a substrate for evaluation of sensitivity, resolution, and adhesion, the surface was wet buff roll polished (manufactured by 3M Co., Ltd., Scotch Bright ) HD # 600, 2 consecutive times).

The board | substrate for evaluation prepared the thing which carried out the jet scrub grinding | polishing (made by Nippon Grinding Abrasive Co., Ltd., Sakurundom A (registered trademark) # F220P) by spray pressure 0.20 Mpa.

<Laminate>

While peeling the polyethylene film of the photosensitive resin laminated body, it laminated at the roll temperature of 105 degreeC using the hot roll laminator (Asahi Chemical Co., Ltd. product, AL-70) to the copper clad laminated board preheated at 60 degreeC after the said board | substrate front surface. . The air pressure was 0.35 MPa, and the lamination speed was 1.5 m / min.

<Exposure>

The mask film required for evaluation of the photosensitive resin layer is placed on a polyethylene terephthalate film serving as a support, and six stages are cured in a 21-step step tablet manufactured by a woofer by an ultra-high pressure mercury lamp (Ohm Manufacturing, HMW-201KB). It exposed by the exposure amount (the unit in Tables 2 and 3 is a step tablet stage number).

<Phenomena>

After peeling the polyethylene terephthalate film, an alkali developing device of (Fuji pore production, the dry film developing device for) and spray a 1 mass% Na ₂ CO ₃ aqueous solution for 30 ℃ at a given time, photosensitive resin layer by using, the photosensitive resin layer The unexposed portions were dissolved away at twice the minimum developing time. At this time, the minimum time required for complete dissolution of the photosensitive resin layer of the unexposed part was made into the minimum developing time.

2. Evaluation method

(1) sensitivity evaluation

The board | substrate for sensitivity and resolution evaluation which passed 15 minutes after lamination was exposed using the 21-step tablet manufactured by Starwoor whose brightness changes by 21 steps from transparent to black. After exposure, development was carried out at a development time twice that of the minimum development time, and the number of step tablets in which the resist film remained completely was used as the sensitivity value.

(2) resolution evaluation

The board | substrate for resolution evaluation which passed 15 minutes after lamination was exposed through the line pattern mask whose width of an exposure part and an unexposed part is a ratio of 1: 1. It developed at the developing time twice the minimum developing time, the minimum mask width in which the hardening resist line was normally formed was made into the resolution value, and resolution was classified as follows.

A: The value of the resolution is 30 micrometers or less.

B: The value of the resolution exceeded 30 micrometers and 40 micrometers or less.

C: The value of the resolution exceeds 40 micrometers.

(3) adhesion evaluation

The sensitivity and the board | substrate for evaluation of resolution which passed 15 minutes after lamination were exposed through the line pattern mask whose width of an exposure part and an unexposed part is 1: 1. It developed at the developing time twice the minimum developing time, and set the minimum mask line width in which the hardening resist line is normally formed as adhesive value.

A: The adhesiveness value is 30 micrometers or less.

B: The value of adhesiveness is more than 30 micrometers and 40 micrometers or less.

C: The adhesiveness value exceeds 40 micrometers.

(4) Peelability Evaluation

The substrate for peelability evaluation which passed 15 minutes after lamination was exposed through the mask which has a pattern of 6 cmx6 cm. After developing at the developing time twice the minimum developing time, it was immersed in 50 degreeC and 3 wt% of caustic soda aqueous solution, the time which a resist film peels was measured, and it classified into ranks as follows.

A: Peeling time is 45 seconds or less.

B: The peeling time exceeds 45 seconds and 50 seconds or less.

C: Peeling time exceeds 50 seconds.

(5) tentability evaluation

The photosensitive resin laminate is laminated on both sides of a substrate having a diameter of 6 mm in a copper clad laminate having a thickness of 1.6 mm, exposed at an exposure dose defined in Tables 2 and 3, and developed at a development time four times the minimum development time. It washed with water and dried. The hole breaking number was measured, and the tent film breaking rate was calculated by the following equation.

Tensile membrane breakage rate (%) = [hole breakage (pieces) / total hole breakage (pieces)] × 100

According to this tent film breaking rate (%), the rank was classified as follows.

A: less than 3%

B: 3% or more but less than 10%

C: 10% or more

3. Evaluation result

The evaluation result of an Example and a comparative example is shown to Tables 2 and 3.

P-1 Has a composition of methyl methacrylate / methacrylic acid / styrene (polymerization ratio 50/25/25),
35 mass% methylethylketone solution of a copolymer having an acid equivalent of 344 and a weight average molecular weight of 50,000 P-2 Has a composition of methyl methacrylate / methacrylic acid / n-butyl acrylate (mass ratio is 65/25/10),
30 mass% methylethylketone solution of a copolymer having an acid equivalent of 344 and a weight average molecular weight of 120,000 P-3 Has a composition of benzyl methacrylate / methyl methacrylate / 2-ethylhexyl acrylate (mass ratio 65/25/10),
50 mass% methylethylketone solution of a copolymer having an acid equivalent of 344 and a weight average molecular weight of 50,000. M-1 Urethane compounds of hexamethylene diisocyanate with monomethacrylate having an average of 5 mol of propylene glycol chain M-2 Dimethacrylate of polyalkylene glycol added with an average of 3 mol each of ethylene oxide to both ends of polypropylene glycol to which an average of 12 mol of propylene oxide was added. M-3 Triacrylate with an average of 3 moles of ethylene oxide added to trimethylolpropane (Shin-Nakamura Chemical A-TMPT-3EO, product name) M-4 4-nonylphenylheptaethylene oxide dipropylene oxide acrylate (LS-100A manufactured by Nippon Oil Holding Co., Ltd.) M-5 Dimethacrylate with an average of 4 moles of ethylene oxide added M-6 (2,2-bis {4- (methacryloxypentaethyleneoxide) phenyl} propane (BPE-500 manufactured by Shin-Nakamura Chemical Corporation, product name) M-7 Dimethacrylate of polyalkylene glycol with an average of 2 moles of propylene oxide and an average of 15 moles of ethylene oxide added to both sides of bisphenol A, respectively. I-1 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer I-2 4,4'-bis (diethylamino) benzophenone D-1 Diamond green D-2 Leuco crystal violet K-1 Polyoxyethylene {tris (1-phenylethyl)} phenyl ether with an average of 18 mol of ethylene oxide added K-2 Polyoxyethylene {tris (1-phenylethyl)} phenyl ether with an average of 8 moles of ethylene oxide added K-3 Polyoxyethylene {tris (1-phenylethyl)} phenyl ether with an average of 15 mol of ethylene oxide added K-4 Polyoxyethylene {tris (1-phenylethyl)} phenyl ether with an average of 28 mol of ethylene oxide added K-5 Polyethyleneglycol-polypropyleneglycol-polyethyleneglycol block copolymer having a polymerization ratio of ethylene oxide / propylene oxide of 40/60

Industrial availability

The photosensitive resin composition of this invention is a metal foil precision process, such as manufacture of a printed wiring board, manufacture of a lead frame for IC chip mounting, manufacture of a metal mask, manufacture of a package, such as BGA or CSP, manufacture of a tape substrate, such as COF and TAB, and a semiconductor bump. The present invention can be suitably applied to the production of partition walls of flat panel displays such as manufacturing, ITO electrodes, address electrodes, electromagnetic shields, and the like.

Claims (16)

20-60 thermoplastic equivalents polymerized using the following (a)-(d) component and (a) at least the (alpha), (beta)-unsaturated carboxyl group-containing monomer as a polymerization component, and a weight average molecular weights 5,000-500,000. 90 mass%, (b) 3-75 mass% addition polymerizable monomer which has at least 1 polymerizable ethylenically unsaturated bond in a molecule, (c) 0.01-30 mass% of photoinitiators, and (d) the following general formula ( Ⅰ):
[Formula 1]

(Wherein, R ₁ to R ₅ are each independently H, an aryl group or an arylalkyl group, and at least one of R ₁ to R ₅ is an aryl group or an arylalkyl group, and A ¹ is C ₂ H ₄ or C ₃ H ₆ and, n ₁ is 2, a plurality of a ¹ are each other may be the same or different or more, and n ₁ is a photosensitive resin composition containing a compound represented by an integer from 1 to 50). The method of claim 1,
The photosensitive resin composition whose at least 1 of R <_1> -R <_5> in the said General formula (I) is a phenylalkyl group. The method of claim 2,
The photosensitive resin composition whose carbon number of the alkyl group part in the said phenylalkyl group is 1-6. The method according to any one of claims 1 to 3,
The photosensitive resin composition whose 1-3 groups of R <_1> -R <_5> in the said General formula (I) are an aryl group or an arylalkyl group, respectively. The method according to any one of claims 1 to 3,
The photosensitive resin composition whose 2 or 3 groups of R <_1> -R <_5> in the said General formula (I) are an aryl group or an arylalkyl group, respectively. 6. The method according to any one of claims 1 to 5,
The photosensitive resin composition whose n <_1> is an integer of 1-35 in the said General formula (I). The method according to any one of claims 1 to 6,
R ₁ to R ₅ in the general formula (I) are each independently H, a phenyl group or a 1-phenylethyl group, two of R ₁ to R ₅ are H, and three of R ₁ to R ₅ are each independently a phenyl group Or 1-phenylethyl group. The method according to any one of claims 1 to 7,
The photosensitive resin composition whose content of the said (d) component is 1-20 mass% when the total amount of the said (a), (b) and (c) component is 100 mass%. The method according to any one of claims 1 to 8,
As said (b) component, the following general formula (II):
(2)

(Wherein R ₆ and R ₇ are each independently H or CH ₃ , and n ₂ , n ₃ and n ₄ are each independently an integer of 3 to 20) or the following general formula (III):
(3)

(Wherein R ₈ and R ₉ are each independently H or CH ₃ , A ² is C ₂ H ₄ , A ³ is C ₃ H ₆ , and n ₅ and n ₆ are each independently 1-29 Is an integer, n ₅ + n ₆ is an integer of 2 to 30, n ₇ and n ₈ are each independently an integer of 0 to 29, and n ₇ + n ₈ is an integer of 0 to 30,-(A ² -O) The arrangement of the repeating units of-and-(A ³ -O)-may be random or a block, and in the case of a block, any of-(A ² -O)-and-(A ³ -O)-is a bisphenyl group side The photosensitive resin composition containing the unsaturated compound which can be photopolymerized by the above) may be used. The photosensitive resin laminated body formed by laminating | stacking the photosensitive resin composition of any one of Claims 1-9 on a support body. The lamination process of forming the photosensitive resin laminated body of Claim 10 on a board | substrate, the exposure process which exposes to the said photosensitive resin laminated body, and the unexposed part of the photosensitive resin in the said photosensitive resin laminated body are removed, and a resist pattern is removed. A resist pattern formation method including the developing process to form. The lamination process of forming the photosensitive resin laminated body of Claim 10 on the board | substrate which is a metal plate or a metal film insulation plate, the exposure process which exposes to the said photosensitive resin laminated body, and the unexposed part of the photosensitive resin in the said photosensitive resin laminated body. And a developing step of removing the resist to form a resist pattern, and forming a conductor pattern by etching or plating the substrate on which the resist pattern is formed. The lamination process of forming the photosensitive resin laminated body of Claim 10 on the board | substrate which is a copper clad laminated board or a flexible substrate, the exposure process which exposes to the said photosensitive resin laminated body, and the photosensitive resin in the said photosensitive resin laminated body. And a step of etching or plating the substrate on which the resist pattern is formed, and the step of peeling the resist pattern from the substrate. The lamination process of forming the photosensitive resin laminated body of Claim 10 on the board | substrate which is a metal plate, the exposure process which exposes to the said photosensitive resin laminated body, and the unexposed part of the photosensitive resin in the said photosensitive resin laminated body, and removing a resist. And a step of etching a substrate on which the resist pattern is formed, and a step of peeling the resist pattern from the substrate. The lamination process of forming the photosensitive resin laminated body of Claim 10 on the board | substrate which is a glass substrate which apply | coated the glass rib paste, the exposure process which exposes to the said photosensitive resin laminated body, and the photosensitive resin in the said photosensitive resin laminated body. A method for producing a substrate having a concave-convex pattern, which includes a developing step of removing an unexposed portion to form a resist pattern, a step of sandblasting the substrate on which the resist pattern is formed, and a step of peeling the resist pattern from the substrate. . The lamination process of forming the photosensitive resin laminated body of Claim 10 on the board | substrate which is a wafer in which the circuit formation as LSI was completed, the exposure process which exposes to the said photosensitive resin laminated body, and the minnow of the photosensitive resin in the said photosensitive resin laminated body. And a step of plating the substrate on which the resist pattern is formed, and a step of peeling the resist pattern from the substrate.