TWI412884B - Photosensitive resin composition, photosensitive resin laminate, photoresist pattern forming method and manufacturing method of conductor pattern, printed wiring board, lead frame, substrate and semiconductor package - Google Patents

Abstract

A photosensitive resin composition providing excellent resolution, adhesion, tinting properties and releasability.  The photosensitive resin composition contains (a) a thermoplastic polymer obtained by polymerizing, as a polymerization component, at least a,ß-unsaturated carboxyl group-containing monomer, and having an acid equivalent weight of 100-600 and a weight average molecular weight of 5,000-500,000, (b) an addition-polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in each molecule, (c) a photopolymerization initiator and (d) a compound represented by general formula (I). (In the formula, R1-R5 independently represent an H, an aryl group or an arylalkyl group, and at least one of R1-R5 represents an aryl group or an arylalkyl group; A1 represents C2H4 or C3H6, and when n1 is not less than 2, the plurality of A1's may be the same as or different from each other; and n1 represents an integer of 1-50.)

Description

Photosensitive resin composition, photosensitive resin laminate, photoresist pattern forming method, conductor pattern, printed wiring board, lead frame, substrate, and semiconductor package manufacturing method

The present invention relates to a photosensitive resin composition which can be developed by using an aqueous alkaline solution, a photosensitive resin laminate obtained by laminating the photosensitive resin composition on a support, and formed on the substrate using the photosensitive resin laminate. A method of a photoresist pattern and the use of the photoresist pattern. More specifically, the present invention relates to a photosensitive resin composition capable of forming a photoresist pattern suitable for fabrication: a printed wiring board; a flexible printed wiring board; IC (integrated circuit) Circuit) manufacturing of lead frame for wafer mounting (hereinafter referred to as lead frame); precision processing of metal foil such as metal mask manufacturing; BGA (Ball Grid Array) or CSP (Chip Size Package) Manufacturing of a semiconductor package; a tape reel represented by TAB (Tape Automated Bonding) or COF (Chip On Film); a semiconductor IC mounted on a film-shaped micro wiring board) Fabrication of a substrate; fabrication of a semiconductor bump; fabrication of an ITO (Indium Tin Oxide) electrode, an address electrode, or an electromagnetic wave mask in the field of flat panel displays.

Previously, printed wiring boards were manufactured by photolithography. In the photolithography method, a photosensitive resin composition is applied onto a substrate, and pattern exposure is performed to thermally cure the exposed portion of the photosensitive resin composition, and the unexposed portion is removed using a developing solution to form a substrate. After forming a photoresist pattern on the substrate and etching or plating the substrate to form a conductor pattern, the photoresist pattern is peeled off from the substrate, whereby a conductor pattern can be formed on the substrate.

In the photolithography method, when the photosensitive resin composition is applied onto a substrate, any one of the following methods may be employed: a solution of the photosensitive resin composition is applied onto a substrate to be dried; or A layer of a photosensitive resin laminate (hereinafter also referred to as "dry film photoresist") having a support layer, a layer containing a photosensitive resin composition (hereinafter also referred to as "photosensitive resin layer"), and an optional protective layer is laminated. On the substrate. Moreover, in the manufacture of printed wiring boards, the latter dry film photoresist is often used.

Hereinafter, a method of manufacturing a printed wiring board using the above dry film photoresist will be briefly described. First, when the dry film photoresist has a protective layer such as a polyethylene film, it is peeled off from the photosensitive resin layer. Then, the photosensitive resin layer and the support are laminated on the substrate such as a copper clad laminate by using a laminator so as to form the substrate, the photosensitive resin layer, and the support. Then, the photosensitive resin layer is exposed by ultraviolet rays such as i-line (365 nm) emitted from an ultrahigh pressure mercury lamp through a mask having a wiring pattern, whereby the exposed portion is polymerized and cured. Next, the support containing polyethylene terephthalate or the like is peeled off. Then, the unexposed portion of the photosensitive resin layer is dissolved or dispersed by a developing solution such as a weakly alkaline aqueous solution to form a photoresist pattern on the substrate. Then, a known etching process or a pattern plating process is performed using the formed photoresist pattern as a protective mask. In the method of removing the metal portion by etching, the through hole of the substrate or the via hole for interlayer connection is covered with the cured photoresist film so that the metal in the hole is not etched. This method is called the cover hole method. In the etching step, for example, a solution of copper chloride, iron chloride or copper ammonia complex can be used. Finally, the photoresist pattern is peeled off from the substrate by an alkaline aqueous solution such as sodium hydroxide to produce a printed wiring board which is a substrate having a conductor pattern. As for the peeling speed, in terms of workability, workability, and productivity, it is preferred that the peeling speed is fast.

On the other hand, with the miniaturization of wiring intervals in printed wiring boards in recent years, there is an increasing demand for high resolution of dry film photoresist. Further, in the capping method and the plating method, in order to prevent the etching liquid and the plating solution from being infiltrated between the photoresist and the copper, the adhesion between the photoresist and the copper is important, but the adhesion is improved. The problem that the peeling time becomes longer.

In Patent Document 1, a photosensitive resin composition containing a chain copolymer of ethylene oxide and propylene oxide is described in order to maintain high resolution and high adhesion of the photosensitive resin composition and to improve capping properties. The issue of peelability is not described.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-20726

Therefore, the photosensitive resin composition for dry film is not provided with a photosensitive resin which is excellent in resolution, adhesion, and capping property, and which has a large peeling speed, which contributes greatly to workability, workability, and productivity. combination.

An object of the present invention is to provide a photosensitive resin composition which is excellent in resolution, adhesion, and capping property and which has excellent releasability by using an alkaline aqueous solution of a cured photoresist film, and the photosensitivity of the photosensitive resin composition is used. A resin laminate, a photoresist pattern forming method for forming a photoresist pattern on a substrate using the photosensitive resin laminate, and a conductor pattern, a printed wiring board, a lead frame, a substrate, and a semiconductor package using the photosensitive resin laminate Production method.

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

[1] A photosensitive resin composition comprising the following components (a) to (d): (a) 20 to 90% by mass of a thermoplastic polymer, which contains at least an α, β-unsaturated carboxyl group The monomer is obtained by polymerizing a polymerization component, having an acid equivalent weight of 100 to 600 and a weight average molecular weight of 5,000 to 500,000; (b) an addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule 3 ~75 mass%; (c) photopolymerization initiator 0.01 to 30% by mass; and (d) a compound represented by the following formula (I):

[Chemical 1]

(wherein R ₁ to R ₅ are each independently H, aryl or aralkyl, and at least one of R ₁ to R ₅ is an aryl group or an aralkyl group, and A ¹ is C ₂ H ₄ or C ₃ When H ₆ and n ₁ are 2 or more, a plurality of A ^{1 's} may be the same or different from each other, and n ₁ is an integer of 1 to 50).

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

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

[4] The photosensitive resin composition according to any one of the above [1] to [3] wherein, in the above formula (I), 1 to 3 of R ₁ to R ₅ are each an aryl group or an aromatic group. alkyl.

[5] The photosensitive resin composition according to any one of the above [1] to [3] wherein, in the above formula (I), 2 or 3 of R ₁ to R ₅ are each an aryl group or an aromatic group. alkyl.

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

[7] The photosensitive resin composition according to any one of the above [1] to [6] wherein R ₁ to R ₅ in the above formula (I) are each independently H, phenyl or 1-phenyl The base, two of R ₁ to R ₅ are H, and three of R ₁ to R ₅ are each independently a phenyl group or a 1-phenylethyl group.

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

[9] The photosensitive resin composition according to any one of the above [1] to [8], wherein the component (b) contains the following formula (II):

[Chemical 2]

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

[Chemical 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 an integer from 1 to 29 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 arrangement of the repeating units may be random or block, and in the case of a block, either -(A ² -O)- and -(A ³ -O)- may be double Photopolymerizable unsaturated compound represented by phenyl side).

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

[11] A photoresist pattern forming method comprising: a laminating step of forming a photosensitive resin laminate according to the above [10] on a substrate; an exposing step of exposing the photosensitive resin laminate; and a developing step The unexposed portion of the photosensitive resin in the photosensitive resin laminate is removed to form a photoresist pattern.

[12] A method of producing a conductor pattern, comprising: a laminating step of forming a photosensitive resin laminate according to [10] above on a substrate of a metal plate or a metal film insulating plate; and an exposure step of the photosensitive resin The laminate is exposed; the developing step removes the unexposed portion of the photosensitive resin in the photosensitive resin laminate to form a photoresist pattern; and etching or plating the substrate on which the photoresist pattern is formed, thereby forming The step of the conductor pattern.

[13] A method of producing a printed wiring board, comprising: a laminating step of forming a photosensitive resin laminate of the above [10] on a substrate of a copper clad laminate or a flexible substrate; and an exposing step The photosensitive resin laminate is exposed; the developing step removes the unexposed portion of the photosensitive resin in the photosensitive resin laminate to form a photoresist pattern; and the step of etching or plating the substrate on which the photoresist pattern is formed And a step of stripping the photoresist pattern from the substrate.

[14] A method of manufacturing a lead frame, comprising: a laminating step of forming a photosensitive resin laminate according to [10] above on a substrate of a metal plate; and exposing, exposing the photosensitive resin laminate; a developing step of removing an unexposed portion of the photosensitive resin in the photosensitive resin laminate to form a photoresist pattern; etching a substrate on which the photoresist pattern is formed; and stripping the photoresist pattern from the substrate The steps.

[15] A method for producing a substrate, wherein the substrate has a concave-convex pattern, the method comprising: a laminating step of forming the photosensitive resin laminate according to [10] above, which is coated with a glass rib rubber. On the substrate of the glass substrate; exposing the photosensitive resin laminate to an exposure step; and developing a step of removing the unexposed portion of the photosensitive resin in the photosensitive resin laminate to form a photoresist pattern; a step of performing a sandblasting process on the substrate of the resist pattern; and a step of peeling the photoresist pattern from the substrate.

[16] A method of manufacturing a semiconductor package, comprising: a laminating step of forming a photosensitive resin laminate according to the above [10] on a circuit that has been completed as an LSI (Large-scale Integrated Circuit) a substrate on the formed wafer; an exposure step of exposing the photosensitive resin laminate; and a developing step of removing the unexposed portion of the photosensitive resin in the photosensitive resin laminate to form a photoresist pattern; a step of plating the substrate of the photoresist pattern; and a step of peeling the photoresist pattern from the substrate.

According to the present invention, it is possible to provide a photosensitive resin composition which is excellent in resolution, adhesion, and capping property and which has excellent releasability by using an alkaline aqueous solution of a cured photoresist film, and the photosensitivity of the photosensitive resin composition is used. A resin laminate, and a method of forming a high-fine photoresist pattern using the photosensitive resin laminate. Further, by using the photosensitive resin laminate, a high-definition printed wiring board, a lead frame, and a semiconductor package can be manufactured, and a flat panel display can be manufactured.

Hereinafter, the present invention will be specifically described.

<Photosensitive Resin Composition>

The photosensitive resin composition of the present invention contains the following components (a) to (d) as essential components: (a) a monomer having at least an α,β-unsaturated carboxyl group as a polymerization component, and an acid equivalent of 100 ~600, and a thermoplastic polymer having a weight average molecular weight of 5,000 to 500,000 (hereinafter also referred to as (a) thermoplastic polymer) 20 to 90% by mass; (b) having at least one polymerizable ethylenically unsaturated bond in the molecule Addition polymerizable monomer (hereinafter also referred to as (b) addition polymerizable monomer) 3 to 75% by mass; (c) Photopolymerization initiator (hereinafter also referred to as (c) photopolymerization initiator) 0.01 to 30% by mass; and (d) to the following formula (I):

[Chemical 4]

(wherein R ₁ to R ₅ are each independently H, aryl or aralkyl, and at least one of R ₁ to R ₅ is an aryl group or an aralkyl group, and A ¹ is C ₂ H ₄ or C ₃ H ₆ , when n ₁ is 2 or more, a plurality of A ^{1 's} may be the same or different, and n ₁ is an integer represented by 1 to 50) (hereinafter, also referred to as (d) is a formula (I) The compound indicated).

(a) Thermoplastic polymer

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

(a) The carboxyl group in the thermoplastic polymer is required for the developer or the release liquid containing the alkaline aqueous solution to have developability or releasability in the photosensitive resin composition of the present invention. (a) The thermoplastic polymer has an acid equivalent of from 100 to 600, preferably from 250 to 450. With respect to the acid equivalent, the acid equivalent is ensured from the viewpoint of (a) the compatibility of the thermoplastic polymer with the solvent or other components in the photosensitive resin composition, particularly the (a) addition polymerizable monomer described later. 100 or more, the acid equivalent is 600 or less from the viewpoint of maintaining developability or peelability. The acid equivalent herein means the mass (gram) of the thermoplastic polymer having 1 equivalent of a carboxyl group. Further, the measurement of the acid equivalent can be carried out, for example, by using a Hiranuma Reporting Titrator (COM-555) using a 0.1 mol/L NaOH aqueous solution by potentiometric titration.

(a) The thermoplastic polymer has a weight average molecular weight of 5,000 to 500,000. With respect to the weight average molecular weight, the thickness of the photosensitive resin laminate (that is, the dry film photoresist) is maintained to be uniform, and from the viewpoint of obtaining resistance to the developer, it is 5,000 or more, and the viewpoint of maintaining developability is maintained. In terms of 500,000 or less. It is preferred that the weight average molecular weight is 20,000 to 100,000. The weight average molecular weight in the present specification means a weight average measured by a gel permeation chromatography (GPC) using a calibration curve of polystyrene (for example, Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd.). Molecular weight. The weight average molecular weight can be measured under the following conditions using a gel permeation chromatography instrument manufactured by JASCO Corporation.

Differential Refractometer: RI-1530

Pump: PU-1580

Degasser: DG-980-50

Column oven: CO-1560

Column: in order, KF-8025, KF-806M×2, KF-807

Dissolution: THF (tetrahydrofuran, tetrahydrofuran)

In the (a) thermoplastic polymer, from the viewpoint of image formation property after alkali development, a polymer of one type of the first monomer described later, a copolymer of two or more kinds, or a second single described later is preferred. A polymer of one type or a copolymer of two or more types, or a copolymer of one or more of the first monomers and one or more of the second monomers.

A carboxylic acid or anhydride having one polymerizable unsaturated group in the first single system molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among them, (meth)acrylic acid is particularly preferable from the viewpoint of developability of the alkali solution. Here, the (meth)acryl group means a propenyl group or a methacryl group. The same is true below.

The second single system is a monomer which is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid ring Ethyl alcohol esters such as hexyl ester, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, vinyl acetate, (meth)acrylonitrile, styrene, and polymerizable styrene derivatives . Among them, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are particularly preferable from the viewpoint of image formability.

More specific examples of the (a) thermoplastic polymer include a polymer containing methyl methacrylate, methacrylic acid, and styrene as a copolymerization component, and include methyl methacrylate, methacrylic acid, and n-butyl acrylate. A polymer having an ester as a copolymerization component, and a polymer containing benzyl methacrylate, methyl methacrylate and 2-ethylhexyl acrylate as a copolymerization component.

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

(b) Addition polymerizable monomer

(b) The addition polymerizable monomer has at least one polymerizable ethylenically unsaturated bond in the molecule. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group from the viewpoint of good image formability. From the viewpoint of high resolution and suppression of edge melting, it is preferred to contain at least one of photopolymerizable unsaturated compounds represented by the following general formula (II) or (III) as (b) A polymerizable monomer.

[Chemical 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)

[Chemical 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 an integer from 1 to 29 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 arrangement of the repeating units may be random or block, and in the case of a block, either -(A ² -O)- and -(A ³ -O)- may be double Phenyl side)

In the compound represented by the above formula (II), n ₂ , n ₃ and n ₄ are each independently 3 or more and 20 or less. In the case of n ₂ , n ₃ and n ₄ , it is 3 or more in terms of improving the capping property, and is 20 or less in terms of improving the sensitivity and the resolution. More preferably, n ₂ and n ₄ are each independently 3 or more and 10 or less, and n ₃ is 5 or more and 15 or less.

In the compound represented by the above formula (III), n ₅ and n ₆ are each independently an integer of from 1 to 29, and n ₅ + n ₆ is an integer of from 2 to 30. In the viewpoint of the flexibility of the cured photoresist film, n ₅ and n ₆ are 1 or more, and 29 or less from the viewpoint of obtaining sufficient sensitivity. n ₅ + n ₆ is 2 or more from the viewpoint of the capping property, and is 30 or less from the viewpoint of image formability. Further, in the compound represented by the above 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. For n ₇ and n ₈ , it is 29 or less from the viewpoint of obtaining sufficient sensitivity. With respect to n ₇ + n ₈ , it is 30 or less from the viewpoint of developer agglutinability.

In the compound represented by the above formula (III), the value of n ₅ + n ₆ + n ₇ + n ₈ is preferably 2 or more, and preferably 40 or less. The above value is preferably 2 or more from the viewpoint of the flexibility and the capping property of the cured photoresist film obtained by curing the photosensitive resin composition, and the above value is preferable for the effect of the resolution. 40 or less. Specific examples of the unsaturated compound represented by the above formula (III) include a dimethyl group of polyethylene glycol obtained by adding an average of 2 moles of ethylene oxide to both ends of bisphenol A. Acrylate (such as NK Ester BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.), polyethylene glycol dimethacrylate obtained by adding an average of 5 moles of ethylene oxide to both ends of bisphenol A Ester (such as NK Ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.), and an average of 6 moles of ethylene oxide and an average of 2 moles of propylene oxide on both ends of bisphenol A Dimethacrylate of alkanediol, dimethacrylate of polyalkylene glycol obtained by adding an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide to both ends of bisphenol A Wait.

As for the ratio of the photopolymerizable unsaturated compound represented by the above formula (II) to (b) the addition polymerizable monomer, the sensitivity, the resolution, the adhesion and the capping property are improved. In particular, it is preferably 3% by mass or more, and is preferably 70% by mass or less from the viewpoint of suppressing edge melting. The above ratio is more preferably 3% by mass or more and 50% by mass or less, and still more preferably 3% by mass or more and 30% by mass or less.

The ratio of the photopolymerizable unsaturated compound represented by the above formula (III) to (b) the addition polymerizable monomer is preferably 3% by mass in terms of sensitivity. From the above, from the viewpoint of suppressing edge melting, it is preferably 70% by mass or less. The above ratio is preferably from 10 to 65% by mass, and more preferably from 15 to 55% by mass.

The (b) addition polymerizable monomer used in the photosensitive resin composition of the present invention may have at least one polymerizable addition to the compounds represented by the above formulas (II) and (III). A well-known compound of an ethylenically unsaturated bond. Examples of such a compound include 4-mercaptophenylheptaethylene glycol dipropylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxy hexaethylene glycol acrylate, and phthalic acid. a reaction product of a half ester compound of acetic anhydride and 2-hydroxypropyl acrylate and propylene oxide (for example, manufactured by Nippon Shokubai Chemical Co., trade name OE-A200), 4-n-octylphenoxypentapropylene glycol acrylate, 1, 6-hexanediol (meth) acrylate, 1,4-cyclohexanediol di(meth) acrylate, and further, polypropylene glycol di(meth) acrylate and polyethylene glycol di(methyl) Polyoxyalkylene glycol di(meth)acrylate such as acrylate, 2-bis(p-hydroxyphenyl)propane di(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol penta(meth)acrylic acid Ester, trimethylolpropane triglycidyl ether tri(meth)acrylate, 2,2-bis(4-methylpropenyloxypentaethoxyphenyl)propane, hexamethylene diisocyanate and nine A polyfunctional (meth) acrylate containing a urethane group such as a carboxylate of propylene glycol monomethacrylate, and an isomeric cyanate compound Polyfunctional (meth) acrylate. These may be used alone or in combination of two or more.

The amount of the (b) addition polymerizable monomer in the photosensitive resin composition of the present invention is in the range of 3 to 75% by mass, more preferably in the range of 15 to 70% by mass. In the viewpoint of suppressing the curing failure of the photosensitive resin composition and the delay in the development time, the amount is 3% by mass or more, and the amount is 75 mass% or less from the viewpoint of suppressing the cold flow and the cured photoresist peeling retardation. .

(c) Photopolymerization initiator

As the photopolymerization initiator (c), a photopolymerization initiator which is generally used as a photosensitive resin can be suitably used, and particularly preferably a hexaarylbisimidazole (hereinafter also referred to as a triarylimidazolyl dimer) is used. . Examples of the triaryl imidazolyl dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer (hereinafter also referred to as 2,2'-bis(2-chlorobenzene). -4,4',5,5'-tetraphenyl-1,1'-bisimidazole), 2,2',5-tris-(o-chlorophenyl)-4-(3,4-di Methoxyphenyl)-4',5'-diphenylimidazolyl dimer, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)- Diphenylimidazolyl dimer, 2,4,5-tris-(o-chlorophenyl)-diphenylimidazolyl dimer, 2-(o-chlorophenyl)-bis-4,5-(3 , 4-dimethoxyphenyl)-imidazolyl dimer, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetra-(3-methoxy Phenyl)-imidazolyl dimer, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetra-(3-methoxyphenyl )-Imidazolyl dimer, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-imidazolyl Dimer, 2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer, 2,2' - bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-double -(2,3,5-trifluorobenzene -4,4',5,5'-tetra-(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, a 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer is preferably a photopolymerization initiator having a high effect on the resolution and the strength of the cured photoresist film. use. These may be used alone or in combination of two or more.

From the viewpoint of photocuring with good sensitivity, it is preferred to contain an acridine compound and/or a pyrazoline compound as (c) a photopolymerization initiator. Examples of the acridine compound include acridine, 9-phenyl acridine, 9-(4-methylphenyl)acridine, 9-(4-methoxyphenyl)acridine, and 9-(4-hydroxybenzene). Acridine, 9-ethyl acridine, 9-chloroethyl acridine, 9-methoxyacridine, 9-ethoxy acridine, 9-(4-methylphenyl)acridine, 9 -(4-ethylphenyl)acridine, 9-(4-n-propylphenyl)acridine, 9-(4-n-butylphenyl)acridine, 9-(4-tert-butylbenzene Acridine, 9-(4-ethoxyphenyl)acridine, 9-(4-ethylphenylphenyl)acridine, 9-(4-dimethylaminophenyl)acridine, 9 -(4-chlorophenyl)acridine, 9-(4-bromophenyl)acridine, 9-(3-methylphenyl)acridine, 9-(3-tert-butylphenyl)acridine , 9-(3-ethylmercaptophenyl)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 so on. Among them, from the viewpoint of image formability, 9-phenyl acridine is preferred.

Further, as the pyrazoline compound, from the viewpoint of photocuring with good sensitivity, 1-phenyl-3-(4-t-butyl-styryl)-5-(4) is preferred. -T-butyl-phenyl)pyrazoline, 1-(4-(benzoxyl) Zin-2-yl)phenyl)-3-(4-t-butyl-styryl)-5-(4-t-butyl-phenyl)pyrazoline, 1-phenyl-3-( 4-biphenyl)-5-(4-tert-butyl-phenyl)pyrazoline and 1-phenyl-3-(4-biphenyl)-5-(4-t-octyl-benzene Pyrazole and the like.

In addition, examples of the photopolymerization initiator other than the above include 2-ethyl hydrazine, octaethyl hydrazine, 1,2-benzopyrene, 2,3-benzopyrene, and 2-benzene. Base, 2,3-diphenylanthracene, 1-chloroindole, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3- Anthraquinones such as dimethyl hydrazine and 3-chloro-2-methyl hydrazine; benzophenone, micazone [4,4'-bis(dimethylamino)benzophenone] and 4 , aromatic ketones such as 4'-bis(diethylamino)benzophenone; benzoin ethers such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin and ethyl benzoin; benzoin dimethyl condensate Ketone, benzoin diethyl ketal; 9-oxo sulfur a combination of an alkylaminobenzoic acid; and 1-phenyl-1,2-propanedione-2-O-benzoin, and 1-phenyl-1,2-propanedione-2-(O - Ethoxycarbonyl) anthracene esters such as hydrazine. Furthermore, as the above 9-oxygen sulfur A combination of a class and an alkylaminobenzoic acid, for example, ethyl-9-oxygen sulfide Combination with ethyl dimethylaminobenzoate, 2-chloro-9-oxosulfur Combination with ethyl dimethylaminobenzoate and isopropyl-9-oxosulfur In combination with ethyl dimethylaminobenzoate. Further, an N-arylamino acid can also be used. Examples of the N-arylamino acid include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine. Among them, N-phenylglycine is particularly preferable from the viewpoint of an increase in sensitivity.

The amount of the (c) photopolymerization initiator in the photosensitive resin composition is in the range of 0.01 to 30% by mass, preferably in the range of 0.05 to 10% by mass. The amount is 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity when photopolymerization is performed by exposure, and the light is sufficiently transmitted to the bottom surface of the photosensitive resin composition (that is, a portion farther from the light source). The above amount is 30% by mass or less from the viewpoint of obtaining good resolution and adhesion.

(d) a compound represented by the formula (I)

In the photosensitive resin composition of the present invention, one or two or more kinds of (d) are contained in the formula (I):

[Chemistry 7]

(wherein R ₁ to R ₅ are each independently H, aryl or aralkyl, and at least one of R ₁ to R ₅ is an aryl group or an aralkyl group, and A ¹ is C ₂ H ₄ or C ₃ When H ₆ and n ₁ are 2 or more, a plurality of A ^{1 's} may be the same or different from each other, and n ₁ is an integer of 1 to 50)

The compound shown has the advantage of maintaining image formation property and capping property, and shortening the peeling time of the photocured film by the alkaline aqueous solution.

In the formula (I), R ₁ to R ₅ are each independently H, an aryl group or an aralkyl group. In the present specification, the term "aralkyl" means that one hydrogen atom of the alkyl group is substituted by an aryl group. The aryl group is a general term for a residue obtained by removing one hydrogen atom from the core of an aromatic hydrocarbon, and examples thereof include a substituted or unsubstituted phenyl group, a tolyl group, a xylyl group, a naphthyl group, and the like. Base. Examples of the aralkyl group include a phenyl group such as a benzyl group or a phenylethyl group, and a cumyl group. From the viewpoint of good adhesion, a phenylalkyl group is preferred, and more preferably Phenylethyl.

At least one of R ₁ to R ₅ is an aryl group or an aralkyl group. Thereby good adhesion can be obtained. Further, in the case where one to three, particularly two or three, of R ₁ to R ₅ are each an aryl group or an aralkyl group, the resolution and the adhesion become good, and in this point, better.

Further, it is particularly preferred that at least one of R ₁ to R ₅ is a phenylalkyl group.

Further, the combination of R ₁ to R ₅ as follows is preferable from the viewpoint of shortening the peeling time: R ₁ to R ₅ are each independently H, a phenyl group or a 1-phenylethyl group, and R ₁ to R ₅ are each Two of them are H, and three of R ₁ to R ₅ are each independently a combination of a phenyl group or a 1-phenylethyl group. On the other hand, the combination of R ₁ to R ₅ other than the above, that is, the following conditions are preferable, and it is preferable that the development aggregability is good: R ₁ to R ₅ are each independently H, an aryl or aralkyl group, and R ₁ ~ R ₅ at least one of the aryl or aralkyl group, but a combination of R ₁ ~ R ₅ is not the R ₁ ~ R ₅ in the 2 H, and R Three of ₁ to R ₅ are each independently a combination of a phenyl group or a 1-phenylethyl group.

The aralkyl group preferably has an alkyl group having 1 to 6 carbon atoms, and when the carbon number is in the range, the aggregability is better. The above carbon number is preferably 1 to 3.

A ¹ in the formula (I) is C ₂ H ₄ or C ₃ H ₆ , whereby the advantage of good aggregability after development can be obtained.

Formula (I), the repeating units - (A ¹ -O) - the number of repetitions n ₁ is 1 to 50, when n ₁ is 2 or more, plural A ¹ may be the same or different from each other. With respect to n ₁ , from the viewpoint of obtaining good aggregability, it is 1 or more, and from the viewpoint of obtaining good image formability and adhesion, it is 50 or less. From the viewpoint of the adhesion becoming better, it is preferred that n ₁ is an integer of 1 to 35. Furthermore, the repeating unit -(A ¹ -O)- can be repeated in a random or block manner.

When the total amount of the components (a), (b) and (c) is 100% by mass, the content of the compound represented by the formula (I) in the photosensitive resin composition is preferably (d). It is in the range of 1 to 20% by mass, more preferably in the range of 2 to 10% by mass. When the content is 1% by mass or more, the aggregation property of the photosensitive resin composition after development is good, and when it is 20% by mass or less, the developability and image formability are good.

For example, Newcol 610 (manufactured by Nippon Emulsifier Co., Ltd.) and Newcol 610 (80) (manufactured by Nippon Emulsifier Co., Ltd.) can be cited as the compound represented by the formula (I). Newcol 2604 (manufactured by Nippon Emulsifier Co., Ltd.), Newcol 2607 (manufactured by Nippon Emulsifier Co., Ltd.), Newcol 2609 (manufactured by Nippon Emulsifier Co., Ltd.), Newcol 2614 (manufactured by Nippon Emulsifier Co., Ltd.), Newcol 707-F (manufactured by Nippon Emulsifier Co., Ltd.), Newcol 710-F (manufactured by Nippon Emulsifier Co., Ltd.), Newcol 714-F (manufactured by Nippon Emulsifier Co., Ltd.), Newcol 2608-F (Japanese emulsifier shares) Co., Ltd., Newcol 2600-FB (manufactured by Nippon Emulsifier Co., Ltd.), Newcol 2616-F (manufactured by Nippon Emulsifier Co., Ltd.), Newcol 3612-FA (manufactured by Nippon Emulsifier Co., Ltd.), etc. In terms of effectively shortening the peeling time, Newcol 2604 (manufactured by Nippon Emulsifier Co., Ltd.), Newcol 2607 (manufactured by Nippon Emulsifier Co., Ltd.), Newcol are more preferable. 2609 (made by Nippon Emulsifier Co., Ltd.) and Newcol 2614 (made by Nippon Emulsifier Co., Ltd.).

The photosensitive resin composition of the present invention may contain various additives as components other than the above components (a) to (d). Specifically, for example, a coloring matter such as a dye or a pigment can be used. Examples of such a coloring material include phthalocyanine green, crystal violet, methyl orange, Nero blue 2B, Victoria blue, malachite green, basic blue 20, and diamond green.

Further, the photosensitive resin composition may contain a coloring agent so that a visible image can be formed by exposure. Examples of such a coloring agent include a leuco dye, or a dye such as a combination of a fluoran dye and a halide. Examples of the halide include bromopentane, bromoisopentane, brominated isobutylene, ethylene bromide, diphenylbromide, dibromon toluene, dibromomethane, tribromomethylphenylphosphonium, and carbon tetrabromide. , tris(2,3-dibromopropyl)phosphate, trichloroacetamide, iodopentane, iodoisobutane, 1,1,1-trichloro-2,2-bis(p-chlorophenyl) Ethane, hexachloroethane and chlorinated three Compounds, etc.

The content of the coloring matter and the coloring agent in the photosensitive resin composition is preferably from 0.01 to 10% by mass. In terms of obtaining good coloring properties and color developability, the content is preferably 0.01% by mass or more, and the contrast between the exposed portion and the unexposed portion is good, and the storage stability is good. Preferably, it is 10% by mass or less.

Further, in order to improve the thermal stability and storage stability of the photosensitive resin composition, it is preferred that the photosensitive resin composition contains: selected from a radical polymerization inhibitor, a benzotriazole, and a carboxybenzotriene. One or more compounds selected from the group consisting of azoles.

Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, t-butylcatechol, cuprous chloride, and 2,6-di- Tributyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6- Tributylphenol), nitrosophenylhydroxylamine aluminum salt, and diphenylnitrosamine.

Further, examples of the benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and bis(N-2-ethylhexyl)amine. Chiatyl-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole and bis(N-2-hydroxyl) Ethyl)aminomethylene-1,2,3-benzotriazole.

Further, examples of the carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N-(N,N). -di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N , N-di-2-ethylhexyl)amine-extended ethylcarboxybenzotriazole.

In the photosensitive resin composition, the total content of the radical polymerization inhibitor, the benzotriazole, and the carboxybenzotriazole is preferably from 0.01 to 3% by mass, more preferably from 0.05 to 1% by mass. The content is preferably 0.01% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and is preferably 3% by mass in terms of maintaining good exposure sensitivity. the following.

The photosensitive resin composition may optionally contain a plasticizer. Examples of the plasticizer include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, and poly a diol-ester of oxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, etc.; phthalic acid ester such as diethyl phthalate; o-toluenesulfonamide, p-toluene Sulfaguanamine, tributyl citrate, triethyl citrate, ethyl triethyl citrate, tri-n-propyl citrate, tri-n-butyl citrate, and the like.

The content of the plasticizer in the photosensitive resin composition is preferably from 5 to 50% by mass, more preferably from 5 to 30% by mass. The content is preferably 5% by mass or more from the viewpoint of suppressing the development time delay and imparting flexibility to the cured photoresist film, and is preferably 50 mass from the viewpoint of suppressing insufficient hardening or cold flow. %the following.

<Photosensitive Resin Composition Blending Liquid>

When the photosensitive resin composition of the present invention is used as a photosensitive resin composition preparation liquid formed by adding a solvent to the photosensitive resin composition, it can be used in various applications. As a suitable solvent, a ketone represented by methyl ethyl ketone (MEK), and an alcohol, such as methanol, ethanol, and isopropyl alcohol, are mentioned. The amount of the solvent to be added to the photosensitive resin composition is preferably adjusted so that the viscosity of the photosensitive resin composition preparation liquid becomes 500 to 4,000 mPa·sec at 25 °C.

<Photosensitive Resin Laminate>

Moreover, the present invention provides a photosensitive resin laminate which is obtained by laminating the photosensitive resin composition of the present invention as described above on a support. The photosensitive resin laminate may have a protective layer on the surface opposite to the support side of the layer containing the photosensitive resin composition (hereinafter also referred to as a photosensitive resin layer).

As the support, it is desirable to be transparent to the light transmitted from the exposure light source. Examples of such a support include 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, and a polycondensation film. A methyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, a cellulose derivative film, or the like. As such films, those which are extended as needed may be used. The haze of the support is preferably 5 or less. The thickness of the support is advantageous in terms of image formation property and economy when the thickness is thin, but it is preferably used in the range of 10 to 30 μm in order to maintain strength.

When a protective layer is formed 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 smaller than the adhesion between the photosensitive resin layer and the support. The protective layer can be easily peeled off from the photosensitive resin layer. For example, a polyethylene film, a polypropylene film or the like can be preferably used as the protective layer. Further, a film excellent in peeling property disclosed in Japanese Laid-Open Patent Publication No. SHO 59-202457 can be preferably used. The film thickness of the protective layer is preferably from 10 to 100 μm, more preferably from 10 to 50 μm.

The thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably from 5 to 100 μm, more preferably from 7 to 60 μm. The thinner the thickness, the higher the resolution, and the thicker the thickness, the higher the film strength. Therefore, the thickness can be appropriately selected depending on the application.

A method of producing the photosensitive resin laminate of the present invention by sequentially laminating a support, a photosensitive resin layer, and an optional protective layer can be carried out by a conventionally known method.

For example, the photosensitive resin composition of the present invention used in the photosensitive resin layer is prepared by preparing the above-mentioned photosensitive resin composition preparation liquid, and first applying it to a support by a bar coater or a roll coater. After drying, a photosensitive resin layer containing the photosensitive resin composition is laminated on the support. Then, a protective layer is laminated on the photosensitive resin layer as needed. The photosensitive resin laminate can be produced by the above steps.

<Photoresist pattern forming method>

Further, the present invention provides a method for forming a photoresist pattern which is obtained by using the above-described photosensitive resin laminate of the present invention. The photoresist pattern forming method includes: a laminating step of forming a photosensitive resin laminate on a substrate; an exposure step of exposing the photosensitive resin laminate; and a developing step of photosensitive in the photosensitive resin laminate The unexposed portion of the resin is removed to form a photoresist pattern. Hereinafter, a specific example of the photoresist forming method will be described.

First, a lamination step is performed using a laminator. In the case where the photosensitive resin laminate has a protective layer, after the protective layer is peeled off, the photosensitive resin layer is heat-compressed and laminated on the surface of the substrate by a laminator. In this case, the photosensitive resin layer may be laminated only on one side of the surface of the substrate, or may be laminated on both sides as needed. The heating temperature at this time is usually 40 to 160 °C. Further, when the heating and pressure bonding is performed twice or more, the adhesion of the obtained photoresist pattern to the substrate can be improved. In this case, the pressure bonding can be carried out by using a two-stage laminator having two rows of rolls, and the photosensitive resin laminate can be laminated on the substrate by passing the photosensitive resin laminate and the substrate several times through the roll. surface.

Then, the exposure step is performed using an exposure machine. After the support is peeled off as needed, the photosensitive resin layer is exposed by active light through a photomask. The amount of exposure is determined by the illumination of the source and the exposure time. The amount of exposure can be measured using a light meter.

A maskless exposure method can also be used in the exposure step. In the maskless exposure, exposure is performed on the substrate using a direct writing device without using a photomask. As the light source, a semiconductor laser or an ultrahigh pressure mercury lamp having a wavelength of 350 to 410 nm can be used. The engraving pattern can be controlled by a computer, and the exposure amount at this time is determined by the illumination of the exposure light source and the moving speed of the substrate.

Next, the developing step is carried out using a developing device. After the exposure, when the support is present on the photosensitive resin layer, the support is removed. Then, the unexposed portion of the photosensitive resin is developed and removed using a developing solution containing an aqueous alkaline solution to obtain a photoresist pattern. As the alkaline aqueous solution, an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ or the like is preferred. These may be selected in accordance with the characteristics of the photosensitive resin layer, and a Na ₂ CO ₃ aqueous solution having a concentration of 0.2 to 2% by mass is usually used. A surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution. Further, the temperature of the developer in the developing step is preferably maintained at a fixed temperature in the range of 20 to 40 °C.

The photoresist pattern can be obtained by the above steps, and a heating step of 100 to 300 ° C can be performed as the case may be. By performing this heating step, the chemical resistance can be further improved. The heating can be performed by means of hot air, infrared rays or far infrared rays.

<Method for Producing Conductor Pattern, Method for Manufacturing Printed Wiring Board>

Moreover, the present invention provides a method of producing a conductor pattern using the above-mentioned photosensitive resin laminate, and a method of producing a printed wiring board using the above-mentioned photosensitive resin laminate. The method for producing a conductor pattern includes a laminating step of forming the above-mentioned photosensitive resin laminate of the present invention on a metal plate or a metal film insulating plate, for example, a substrate of a copper clad laminate; and exposing the layer to a photosensitive resin Exposing a body; developing a step of removing an unexposed portion of the photosensitive resin in the photosensitive resin laminate to form a photoresist pattern; and forming a substrate on which the photoresist pattern is formed (for example, on a copper clad laminate, a substrate) The copper surface is etched or plated to form a conductor pattern. In the lamination step, the exposure step, and the development step, the same methods and conditions as those described in the photoresist pattern forming method can be preferably employed.

Further, the method for producing a printed wiring board includes a laminating step of forming the above-mentioned photosensitive resin laminate of the present invention on a substrate of a copper clad laminate or a flexible substrate, and an exposure step for a photosensitive resin laminate Exposing; developing step of removing the unexposed portion of the photosensitive resin in the photosensitive resin laminate to form a photoresist pattern; etching or plating the substrate on which the photoresist pattern is formed; and stripping light from the substrate The step of blocking the pattern. Typically, after the lamination step, the exposure step, and the development step are carried out in the same manner and conditions as those described in the method for forming a photoresist pattern, a known method such as etching or plating is used. The exposed substrate is subjected to a treatment, and a peeling step is further performed. The photoresist pattern is peeled off from the substrate by using an aqueous solution having a stronger alkalinity than the developer, whereby a desired printed wiring board can be obtained. The alkaline aqueous solution for peeling (hereinafter also referred to as "peeling liquid") is not particularly limited, and an aqueous solution of NaOH or KOH having a concentration of 2 to 5% by mass is usually used. A small amount of a water-soluble solvent may also be added to the stripping solution. Further, the temperature of the stripping liquid in the stripping step is preferably in the range of 40 to 70 °C.

<Method of manufacturing lead frame>

Further, the present invention provides a method of producing a lead frame using the above-described photosensitive resin laminate of the present invention. The method includes a laminating step of forming the above-mentioned photosensitive resin laminate of the present invention on a substrate of a metal plate, an exposure step of exposing the photosensitive resin laminate, and a developing step of depositing the photosensitive resin laminate The unexposed portion of the photosensitive resin is removed to form a photoresist pattern; the step of etching the substrate on which the photoresist pattern is formed; and the step of stripping the photoresist pattern from the substrate. Typically, a metal plate such as copper, a copper alloy or an iron-based alloy is used as the substrate, and after the lamination step, the exposure step, and the development step are carried out in the same manner and conditions as those described in the method for forming a photoresist pattern, The step of etching the exposed substrate to form a conductor pattern. Thereafter, a peeling step is performed, and the photoresist pattern is peeled off in the same manner as in the above-described method of manufacturing a printed wiring board, whereby a desired lead frame can be obtained.

<Method of Manufacturing Substrate Having Concavo-Concave Pattern>

Further, the present invention provides a method of producing a substrate having a concavo-convex pattern using the above-mentioned photosensitive resin laminate. The method includes a laminating step of forming a photosensitive resin laminate on a substrate coated with a glass ribbed glass substrate, an exposure step of exposing the photosensitive resin laminate, and a developing step of depositing the photosensitive resin laminate The unexposed portion of the photosensitive resin is removed to form a photoresist pattern; the step of sandblasting the substrate on which the photoresist pattern is formed; and the step of stripping the photoresist pattern from the substrate. In the lamination step, the exposure step, and the development step, the same methods and conditions as those described in the photoresist pattern forming method can be preferably employed. The photoresist pattern formed in the method of manufacturing the substrate can be used as a protective mask member when the substrate is processed by sand blasting.

Further, in addition to the glass substrate coated with the glass rib rubber, a substrate such as glass, tantalum wafer, amorphous germanium, polycrystalline germanium, ceramic, sapphire, or metal material may be used. Typically, a photoresist step is formed on a substrate coated with a glass rib paste by a lamination step, an exposure step, and a development step in the same manner as the above-described photoresist pattern forming method. Thereafter, a blasting step is performed, that is, a step of blowing the blasting material from above the formed photoresist pattern, cutting into a target depth, and a peeling step, that is, a portion of the photoresist pattern remaining on the substrate by using an alkaline stripping solution or the like A step of removing from the substrate, whereby a substrate having a fine concavo-convex pattern can be formed on the substrate. As the blasting material used in the blasting step, a known one can be used. For example, fine particles having a particle diameter of about 2 to 100 μm such as SiC, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO, glass, or stainless steel can be used.

<Method of Manufacturing Semiconductor Package>

Further, the present invention provides a method of manufacturing a semiconductor package using the above-described photosensitive resin laminate. The method includes a laminating step of forming the photosensitive resin laminate of the present invention described above on a substrate on which a wafer formed as an LSI circuit is completed, an exposure step of exposing the photosensitive resin laminate, and a developing step And removing the unexposed portion of the photosensitive resin in the photosensitive resin laminate to form a photoresist pattern; a step of plating the substrate on which the photoresist pattern is formed; and a step of peeling the photoresist pattern from the substrate. Typically, after the lamination step, the exposure step, and the development step are carried out in the same manner and conditions as those described in the method for forming a photoresist pattern, the following steps are performed: copper is exposed to the exposed opening portion, A columnar plating such as solder is used to form a conductor pattern. Thereafter, a peeling step is performed, and the photoresist pattern is peeled off in the same manner as in the above-described method of manufacturing a printed wiring board, and further, a step of removing a thin metal layer other than the columnar plating by etching is performed. This makes it possible to obtain the desired semiconductor package.

[Examples]

Hereinafter, the present invention will be further described by way of examples, but the invention is not limited thereto. Hereinafter, the production method of the sample for evaluation of the examples and the comparative examples, the evaluation method of the obtained sample, and the evaluation result will be described.

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

The compound shown in Table 1 was mixed in the parts shown in Tables 2 and 3 to obtain a photosensitive resin composition. Further, in Tables 2 and 3, MEK represents methyl ethyl ketone, and the mass ratio of the composition ratio of the compound other than MEK includes the value of MEK.

1. Production of samples for evaluation

The photosensitive resin laminate of the examples and the comparative examples was produced in the following manner.

<Production of Photosensitive Resin Laminate>

The photosensitive resin compositions of the respective examples and the comparative examples were thoroughly stirred and mixed, and each of the compositions was uniformly applied to a 16 μm-thick polyethylene terephthalate film as a support using a bar coater. The surface was dried in a dryer at 95 ° C for 4 minutes, thereby forming a photosensitive resin layer. The thickness of the photosensitive resin layer was 40 μm.

Then, a polyethylene film having a thickness of 22 μm was bonded to the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated, and a photosensitive resin laminate was obtained.

<Substrate surface adjustment>

As a substrate for evaluation of sensitivity, resolution, and adhesion, a 1.2 mm-thick copper-clad laminate having a laminated copper foil having a thickness of 35 μm was used, and the surface was subjected to wet-polishing roll polishing (manufactured by 3M Co., Ltd.). Scotch-Brite (registered trademark) HD#600, passed 2 times).

The evaluation substrate was prepared by sandblasting (manufactured by Nippon Grinding Co., Ltd., Sakurundum A (registered trademark) #F220P) under a spray pressure of 0.20 MPa.

<Lamination>

The polyethylene film of the photosensitive resin laminate was peeled off, and a photosensitive resin laminate was laminated on the surface of the substrate at a roll temperature of 105 ° C using a heating roll laminator (AL-70, manufactured by Asahi Kasei Co., Ltd.). After adjustment, preheat to a copper clad laminate of 60 °C. The air pressure was set to 0.35 MPa, and the lamination speed was set to 1.5 m/min.

<exposure>

The photomask film required for the evaluation of the photosensitive resin layer was placed on a polyethylene terephthalate film as a support, and an ultrahigh pressure mercury lamp (manufactured by ORC, HMW-201 KB) was used, and a 21-stage stage was produced by Stouffer. The exposure amount of the six-stage hardening in the exposure meter (the number of the stages in the stage exposure meters in Tables 2 and 3) was exposed.

<development>

After peeling off the polyethylene terephthalate film, an alkali developing machine (manufactured by Fuji Machine Co., Ltd., dry film developing machine) was used to spray a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C for a specific time on the photosensitive resin layer. The unexposed portion of the photosensitive resin layer was dissolved and removed by twice the minimum development time. At this time, the minimum time required to completely dissolve the photosensitive resin layer of the unexposed portion was taken as the minimum development time.

2. Evaluation method

(1) Sensitivity evaluation

The substrate for sensitivity and resolution evaluation after 15 minutes after lamination was exposed using a 21-stage stage exposure meter made of Stouffer whose brightness was changed from transparent to black in 21 stages. After the exposure, development was performed at a development time twice the minimum development time, and the number of stage exposure sections in which all of the photoresist film remained was used as the sensitivity value.

(2) Resolution evaluation

The substrate for the evaluation of the resolution after 15 minutes from the lamination was exposed by a line mask having a width ratio of the exposed portion to the unexposed portion of 1:1. The development was performed at a development time twice the minimum development time, and the minimum mask width at which the hardened photoresist line was normally formed was taken as the value of the resolution, and the resolution was classified in the following manner.

A: The resolution is 30 μm or less.

B: The value of the resolution exceeds 30 μm and is 40 μm or less.

C: The value of the resolution exceeds 40 μm.

(3) Adhesion evaluation

The substrate for the sensitivity and resolution evaluation after 15 minutes from the lamination was exposed by a line pattern mask having a width ratio of the exposed portion to the unexposed portion of 1:1. The development was performed at a development time twice the minimum development time, and the minimum mask line width at which the hardened photoresist line was normally formed was used as the value of the adhesion.

A: The value of the adhesion is 30 μm or less.

B: The value of the adhesion is more than 30 μm and 40 μm or less.

C: The value of the adhesion is more than 40 μm.

(4) Stripability evaluation

The substrate for peeling evaluation after 15 minutes from the lamination was exposed by a mask having a pattern of 6 cm × 6 cm. After development was carried out at a development time twice the minimum development time, the film was immersed in a 3 wt% aqueous solution of caustic soda at 50 ° C, and the time at which the photoresist film was peeled off was measured and classified in the following manner.

A: The peeling time is 45 seconds or less.

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

C: The peeling time exceeded 50 seconds.

(5) Cover hole evaluation

The photosensitive resin laminate was laminated on both sides of a substrate having a diameter of 6 mm on a 1.6 mm thick copper clad laminate, and exposed at an exposure amount defined in Tables 2 and 3, with a minimum development time of 4 The development time is doubled, the water is washed, and dried. Then, the number of pore breakages was measured, and the crack ratio of the lidhole film was calculated by the following formula.

Cover hole film breakage rate (%) = [number of hole breaks (pieces) / total number of holes (pieces)] × 100

According to the cover film breaking rate (%), the grade was classified as follows.

A: Less than 3%

B: 3% or more and less than 10%

C: 10% or more

3. Evaluation results

The evaluation results of the examples and comparative examples are shown in Tables 2 and 3.

[Industrial availability]

The photosensitive resin composition of the present invention can be suitably used for the production of a printed wiring board, the manufacture of a lead frame for IC chip mounting, the precision processing of a metal foil such as the manufacture of a metal mask, and the manufacture of a package such as BGA or CSP. The manufacture of a tape substrate such as COF or TAB; the manufacture of a semiconductor bump; and the manufacture of a partition wall of a flat panel display such as an ITO electrode or an address electrode or an electromagnetic wave mask.

Claims (17)

A photosensitive resin composition comprising the following components (a) to (d): (a) 20 to 90% by mass of a thermoplastic polymer, which is a monomer having at least an α, β-unsaturated carboxyl group; The polymerization component is obtained by polymerization, the acid equivalent is 100 to 600, and the weight average molecular weight is 5,000 to 500,000; (b) the addition polymerization monomer having at least one polymerizable ethylenic unsaturated bond in the molecule is 3 to 75 mass. (c) a photopolymerization initiator: 0.01 to 30% by mass; and (d) a compound represented by the following formula (I): (In the formula, at least one of R ₁ to R ₅ is a phenylalkyl group, and A ¹ is C ₂ H ₄ or C ₃ H ₆ , and when n ₁ is 2 or more, plural A ^{1 's} may be the same or different. And n ₁ is an integer from 1 to 50). The photosensitive resin composition of claim 1, wherein the alkyl moiety in the phenylalkyl group has 1 to 6 carbon atoms. The photosensitive resin composition of claim 1 or 2, wherein 2 or 3 of R ₁ to R ₅ in the above formula (I) are each an aryl group or an aralkyl group. The photosensitive resin composition of claim 1 or 2, wherein in the above formula (I), n ₁ is an integer of from 1 to 35. The photosensitive resin composition of claim 1 or 2, wherein R ₁ to R ₅ in the above formula (I) are each independently H, a phenyl group or a 1-phenylethyl group. The photosensitive resin composition of claim 1 or 2, wherein the above (a), (b) When the total amount of the component (c) is 100% by mass, the content of the component (d) is 1 to 20% by mass. The photosensitive resin composition of claim 1 or 2, wherein the component (b) contains a photopolymerizable unsaturated compound represented by the following formula (II) or the following formula (III): (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); (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 an integer from 1 to 29 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 arrangement of the repeating units may be random or block, and in the case of a block, either -(A ² -O)- and -(A ³ -O)- may be double Phenyl side). The photosensitive resin composition of claim 1 or 2, wherein in the above formula (I), n ₁ is an integer of from 1 to 35; and R ₁ to R ₅ in the above formula (I) are each independently H, Phenyl or 1-phenylethyl. The photosensitive resin composition of claim 1 or 2, wherein in the above formula (I), n ₁ is an integer of from 1 to 35; and R ₁ to R ₅ in the above formula (I) are each independently H, When the total amount of the components (a), (b), and (c) is 100% by mass, the content of the component (d) is 1 to 20% by mass. The photosensitive resin composition of claim 1 or 2, wherein in the above formula (I), n ₁ is an integer of from 1 to 35; and R ₁ to R ₅ in the above formula (I) are each independently H, A phenyl group or a 1-phenylethyl group; and the component (b) contains a photopolymerizable unsaturated compound represented by the above formula (II) or the above formula (III). A photosensitive resin laminate which is obtained by laminating a photosensitive resin composition according to any one of claims 1 to 10 on a support. A photoresist pattern forming method comprising: a laminating step of forming a photosensitive resin laminate according to claim 11 on a substrate; an exposing step of exposing the photosensitive resin laminate; and a developing step of sensitizing the photosensitive layer The unexposed portion of the photosensitive resin in the resin laminate is removed to form a photoresist pattern. A method for producing a conductor pattern, comprising: a laminating step of forming a photosensitive resin laminate according to claim 11 on a substrate of a metal plate or a metal film insulating plate; and exposing the photosensitive resin laminate to an exposure step a developing step of removing an unexposed portion of the photosensitive resin in the photosensitive resin laminate to form a photoresist pattern; and etching or plating the substrate on which the photoresist pattern is formed, thereby forming a conductor The steps of the pattern. A method of manufacturing a printed wiring board, comprising: a laminating step of forming a photosensitive resin laminate according to claim 11 on a substrate of a copper clad laminate or a flexible substrate; and an exposing step of laminating the photosensitive resin Exposing a body; developing a step of removing an unexposed portion of the photosensitive resin in the photosensitive resin laminate; forming a photoresist pattern; etching or plating the substrate on which the photoresist pattern is formed; and The step of peeling off the photoresist pattern on the substrate. A method of manufacturing a lead frame, comprising: a laminating step of forming a photosensitive resin laminate according to claim 11 on a substrate of a metal plate; an exposing step of exposing the photosensitive resin laminate; and a developing step; The unexposed portion of the photosensitive resin in the photosensitive resin laminate is removed to form a photoresist pattern; a step of etching the substrate on which the photoresist pattern is formed; and a step of peeling off the photoresist pattern from the substrate. A method for producing a substrate, wherein the substrate has a concave-convex pattern, the method comprising: a laminating step of forming a photosensitive resin laminate according to claim 11 on a substrate coated with a glass ribbed glass substrate An exposure step of exposing the photosensitive resin laminate; and a developing step of removing an unexposed portion of the photosensitive resin in the photosensitive resin laminate to form a photoresist pattern; and performing a substrate on which the photoresist pattern is formed a step of sandblasting processing; and a step of peeling off the photoresist pattern from the substrate. A method of manufacturing a semiconductor package, comprising: a laminating step of forming a photosensitive resin laminate of claim 11 on a completed electric power as an LSI On the substrate of the wafer formed by the road; exposing the photosensitive resin laminate to an exposure step; and developing a step of removing the unexposed portion of the photosensitive resin in the photosensitive resin laminate to form a photoresist pattern; a step of plating the substrate having the photoresist pattern; and a step of peeling off the photoresist pattern from the substrate.