JP2013134360A - Photosensitive resin composition, photosensitive resin laminate, and method for forming resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition achieving plating resistance and developing solution dispersibility both at high levels and having excellent resolution.SOLUTION: The photosensitive resin composition includes (a) 20 to 90 mass% of an alkali-soluble polymer, (b) 5 to 75 mass% of an addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule, (c) 0.01 to 30 mass% of a photopolymerization initiator, and (d) 0.01 to 30 mass% of a compound expressed by a specified structural formula.

Description

  The present invention relates to a photosensitive resin composition, a photosensitive resin laminate, and a resist pattern forming method.

  Conventionally, a printed wiring board is generally manufactured by a photolithography method. The photolithographic method is a method in which a photosensitive resin composition is applied onto a substrate, pattern exposure is performed, and an exposed portion of the photosensitive resin composition is polymerized and cured (in the case of a negative type) or solubilized in a developer (positive). Mold) and unexposed areas (in the case of negative molds) or exposed areas (in the case of positive molds) are removed with a developer to form a resist pattern on the substrate, and etching or plating is performed to form a conductor pattern. After forming, the resist pattern is peeled off from the substrate to form a conductor pattern on the substrate.

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

  The dry film resist is an important element for responding to the increase in the density of printed wiring boards and the expansion of demand, and is required to improve various characteristics as compared with the conventional dry film. For example, Patent Document 1 describes a photosensitive resin composition containing a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a plasticizer having a linear chemical structure.

JP 2004-20726 A

  When an alkali development type dry film resist in which an unexposed portion is dissolved or dispersed with a developing solution such as a weak alkaline aqueous solution is used, an unpolymerized composition is dispersed in the developing solution, and when this dispersion is collected, development is performed. It may become an aggregate in the liquid or cause foaming of the developer. Aggregates reattach to the substrate during the development process and cause defects. In addition, when the developer is circulated through the filter in order to prevent the occurrence of defects, the frequency of filter replacement increases or the cleaning interval of the developing machine becomes shorter if a large amount of aggregates are generated. The problem is occurring. That is, the dry film resist is required to have improved developer dispersibility.

  Furthermore, the dry film resist is required to have both resolution and plating resistance. The photosensitive resin composition described in Patent Document 1 still has room for improvement from the viewpoint of achieving a high level of resolution, plating resistance, and developer dispersibility.

  This invention is made | formed in view of the said situation, and makes it a subject to provide the photosensitive resin composition which is compatible in a metal-plating resistance and a developing solution dispersibility at a high level, and is further excellent in resolution.

  As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by the following technical means.

That is, the present invention is as follows.
[1]
(A) Alkali-soluble polymer 20 to 90% by mass,
(B) 5 to 75% by mass of an addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule;
(C) 0.01-30% by mass of a photopolymerization initiator, and (d) 0.01-30% by mass of a compound represented by the following general formula [I],
The photosensitive resin composition characterized by including.

(In the formula, R ¹ is a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms, A ¹ is an alkylene group having 2 to 10 carbon atoms, n ¹ , n ² , n ³ , Is a number satisfying n ¹ + n ² + n ³ = ^{3 to} 120, and n ⁴ is 0 or 1. In the formula, a plurality of A ^{1 s} may be the same or different, and — (O—A ¹ ) The repeating structure of-may be random or block.)
[2]
The photosensitive resin composition according to [1], wherein the addition polymerizable monomer includes at least one compound selected from the group consisting of compounds represented by the following general formulas [II] to [V].

(In the formula, R ² and R ³ each independently represent a hydrogen atom or a methyl group, A ² represents an alkylene group having 2 to 6 carbon atoms, and n ⁵ and n ⁶ represent n ⁵ + n ⁶ = 2 to 40. (In the formula, a plurality of A ² may be the same or different, and the repeating structure of — (A ² —O) — may be random or block.)

(Wherein R ⁴ represents an alkylene group, R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, A ³ represents an alkylene group having 2 to 6 carbon atoms, and n ⁷ and n ⁸ represent n ⁷ + n ⁸ = 2 to 40. In the formula, a plurality of A ^{3 s} may be the same or different, and the repeating structure of — (A ³ —O) — may be random. It may be a block.)

(Wherein R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, A ⁴ represents an alkylene group having 2 to 6 carbon atoms, and n ⁹ is a number satisfying 2 to 40. A ⁴ present may be the same or different, and the repeating structure of — (A ⁴ —O) — may be random or block.)

(In the formula, R ⁹ represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms, R ¹⁰ , R ¹¹ and R ¹² each independently represents a hydrogen atom or a methyl group, and A ⁵ represents carbon. N ¹³ is 0 or 1. n ¹⁰ , n ¹¹ and n ¹² are numbers satisfying n ¹⁰ + n ¹¹ + n ¹² = 3 to 60. ⁵ may be the same or different, and the repeating structure of-(O-A ⁵ )-may be random or block.)
[3]
The photosensitive resin composition according to [1] or [2], wherein the addition polymerizable monomer includes a compound represented by the following general formula [VI].

(In the formula, R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 15 carbon atoms, R ¹⁴ represents a hydrogen atom or a methyl group, and A ⁶ represents an alkylene group having 2 to ⁶ carbon atoms. , N ¹⁴ is a number satisfying 1 to 30. In the formula, a plurality of A ⁶ may be the same or different from each other, and the repeating structure of — (O—A ⁶ ) — is random or blocked. It may be.)
[4]
The photosensitive resin composition according to any one of [1] to [3], wherein the alkali-soluble polymer includes a styrene monomer structure.
[5]
The photosensitive resin composition according to any one of [1] to [4], wherein the photopolymerization initiator includes 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer.
[6]
The photosensitive resin laminated body containing the photosensitive resin composition layer which consists of the photosensitive resin composition in any one of [1]-[5], and the support layer which supports the said photosensitive resin composition layer.
[7]
A step of laminating the photosensitive resin laminate according to [6] on a substrate, an exposure step of exposing a photosensitive resin layer contained in the photosensitive resin laminate, and an unexposed portion in the photosensitive resin layer after the exposure A resist pattern forming method comprising: a developing step of removing a resist with a developing solution to form a resist pattern.
[8]
The resist pattern forming method according to [7], wherein the exposure step is a step of performing exposure by direct drawing of a drawing pattern.
[9]
A method for forming a conductor pattern using the method for forming a resist pattern according to [7] or [8],
The said board | substrate is a metal plate or a metal-film insulation board, The formation method of a conductor pattern including the process of etching or plating the part which is not coat | covered with the resist pattern of the said board | substrate surface.
[10]
A method for manufacturing a printed wiring board using the method for forming a resist pattern according to [7] or [8],
The substrate is a copper-clad laminate or a flexible substrate, and includes a step of etching or plating a portion of the substrate surface not covered with the resist pattern, and a step of peeling the resist pattern after the etching or plating step. Manufacturing method of printed wiring board.
[11]
A method of manufacturing a lead frame using the resist pattern forming method according to [7] or [8],
A method for manufacturing a lead frame, comprising: an etching step of etching a portion of the substrate surface that is not covered with a resist pattern; and a step of peeling the resist pattern after the etching step.
[12]
A method for manufacturing a semiconductor package using the method for forming a resist pattern according to [7] or [8],
The substrate is a wafer on which an LSI is formed, and includes a plating step of plating a portion of the substrate surface not covered with the resist pattern, and a step of peeling the resist pattern after the plating step. Production method.

  According to the present invention, a photosensitive resin composition having both high plating resistance and developer dispersibility at a high level and having excellent resolution is provided.

  The best mode for carrying out the present invention (hereinafter abbreviated as “embodiment”) will be described in detail below. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

<Photosensitive resin composition>
The photosensitive resin composition in the present embodiment is
(A) Alkali-soluble polymer 20 to 90% by mass,
(B) 5 to 75% by mass of an addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule;
(C) 0.01-30% by mass of a photopolymerization initiator, and (d) 0.01-30% by mass of the compound represented by the general formula [I],
including.

<Alkali-soluble polymer>
The alkali-soluble polymer is typically a thermoplastic copolymer having a weight average molecular weight of 5,000 to 500,000 containing a carboxyl group-containing monomer as a copolymerization component.

  The weight average molecular weight of the thermoplastic copolymer is preferably 5,000 to 500,000. The weight average molecular weight of the thermoplastic copolymer is preferably 5,000 or more from the viewpoint of maintaining the thickness of the dry film resist uniformly and obtaining resistance to the developer, while being 500 from the viewpoint of maintaining developability. 1,000 or less is preferable. The lower limit of the weight average molecular weight of the more preferable thermoplastic copolymer is 20,000, and the upper limit is 300,000. The preferred molecular weight distribution is 1.5-7, the more preferred lower limit is 2, and the upper limit is 5.

  The thermoplastic copolymer is preferably obtained by copolymerizing a copolymer component composed of one or more first monomers described later and one or more second monomers described later.

  The first monomer is a monomer containing a carboxyl group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is particularly preferable. Here, (meth) acryl indicates acryl or methacryl. The same applies hereinafter.

  The second monomer is a monomer that 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, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, vinyl acetate, etc. And (meth) acrylonitrile, styrenic monomers (styrene and polymerizable styrene derivatives), and the like. Of these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are preferred, and styrene is particularly preferred from the viewpoint of resolution.

  The alkali-soluble polymer is prepared by mixing the above monomers and diluting with a solvent such as acetone, methyl ethyl ketone, methanol, ethanol, normal propyl alcohol, or isopropanol, to a radical polymerization initiator such as benzoyl peroxide, The synthesis is preferably carried out by adding an appropriate amount of azoisobutyronitrile and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

  A particularly preferable alkali-soluble polymer has a copolymerization ratio of the first monomer and the second monomer of 10 to 60% by mass of the first monomer and 40 to 90% of the second monomer. The first monomer is 15 to 35% by mass, and the second monomer is 65 to 85% by mass.

  More specific examples of the alkali-soluble polymer include a polymer containing methyl methacrylate, methacrylic acid and styrene as a copolymer component, and a polymer containing methyl methacrylate, methacrylic acid and n-butyl acrylate as a copolymer component. And polymers containing benzyl methacrylate, methyl methacrylate and 2-ethylhexyl acrylate as a copolymerization component.

  In the present embodiment, the content of the alkali-soluble polymer in the photosensitive resin composition (however, based on the total solid content of the photosensitive resin composition. Is the same in the components.) Is in the range of 20% by mass to 90% by mass, the preferred lower limit is 25% by mass, the preferred upper limit is 75% by mass, the more preferred lower limit is 40% by mass, and the more preferred upper limit is 65% by mass. It is. This content is preferably 20% by mass or more from the viewpoint of maintaining alkali developability, and on the other hand, 90% by mass from the viewpoint that the resist pattern formed by exposure sufficiently exhibits the performance as a resist. The following is preferable.

<Addition polymerizable monomer>
The addition-polymerizable monomer is a monomer having addition-polymerizability by having, for example, an ethylenically unsaturated group. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group.

From the viewpoints of high resolution, edge fuse, and tenting, it is preferable to use at least one bisphenol A (meth) acrylate compound as the addition polymerizable monomer. The bisphenol A-based (meth) acrylate compound here means a (meth) acryloyl group or a carbon-carbon unsaturated double bond derived from a (meth) acryloyl group and —C ₆ H ₄ —C (CH derived from bisphenol A ₃ ) A compound having a _2- C ₆ H ₄ -group and represented by the general formula [II].

(In the formula, R ² and R ³ each independently represent a hydrogen atom or a methyl group, A ² represents an alkylene group having 2 to 6 carbon atoms, and n ⁵ and n ⁶ represent n ⁵ + n ⁶ = 2 to 40. (In the formula, a plurality of A ² may be the same or different, and the repeating structure of — (A ² —O) — may be random or block.)
In the compound represented by the general formula [II], A ² represents —CH (CH ₃ ) CH ₂ —, —CH ₂ CH (CH ₃ ) —, and —CH ₂ CH from the viewpoints of resolution and developer dispersibility. It is preferably at least one selected from the group consisting of _2- , and when different alkylene groups are mixed, the repeating structure is preferably a block.

In the compound represented by the general formula [II], n ⁵ + n ⁶ is preferably 2 or more from the viewpoints of flexibility and tenting properties of the cured film, and 40 or less from the viewpoint of material handling properties. Is preferred.
Specific examples of the unsaturated compound represented by the general formula [II] include polyethylene glycol dimethacrylate in which 1 unit of ethylene oxide is added to both ends of bisphenol A and 2 units of average on both ends of bisphenol A, respectively. Polyethylene glycol dimethacrylate with ethylene oxide added, polyethylene glycol dimethacrylate with an average of 5 units of ethylene oxide added to both ends of bisphenol A, and polyethylene glycol with an average of 7 units of ethylene oxide added to both ends of bisphenol A Polyalkylene glycol dimethacrylate, bi-dimethacrylate and bisphenol A each having an average of 6 units of ethylene oxide and an average of 2 units of propylene oxide added. Dimethacrylate phenol A polyalkylene glycols each obtained by adding propylene oxide ethylene oxide and average 2 units of the average 15 units at both ends of the preferred.

  From the viewpoint of plating resistance, edge fuse properties, and cured film flexibility, it is preferable to include at least one compound represented by the general formula [III] as an addition polymerizable monomer.

(Wherein R ⁴ represents an alkylene group, R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, A ³ represents an alkylene group having 2 to 6 carbon atoms, and n ⁷ and n ⁸ represent n ⁷ + n ⁸ = 2 to 40. In the formula, a plurality of A ^{3 s} may be the same or different, and the repeating structure of — (A ³ —O) — may be random. It may be a block.)
In the compound represented by the general formula [III], R ⁴ is preferably an alkylene group having 1 to 9 carbon atoms, and A ³ is —CH (CH ₃ ) CH from the viewpoints of resolution and developer dispersibility. _{2 -, - CH 2 CH (} CH 3) -, and -CH ₂ CH ₂ - is preferably at least one selected from the group consisting of, the repeating structure in the case of different alkylene groups are mixed block It is preferable that

In the compound represented by the general formula [III], n ⁷ + n ⁸ is preferably 2 or more from the viewpoint of flexibility and tenting properties of the cured film, and preferably 40 or less from the viewpoint of resolution. .
Specific examples of the unsaturated compound represented by the general formula [III] include dimethacrylates in which R ⁴ is a hexamethylene group, A ³ is a propylene group, n ⁷ = 1 and n ⁸ = 6, R ⁴ is a hexamethylene group, A ³ is a propylene group, n ⁷ and n ⁸ are 6 dimethacrylates, R ⁴ is a hexamethylene group, A ³ is a propylene group, n ⁷ , n Preference is given to dimethacrylates in which ⁸ is a dimethacrylate of 9 and R ⁴ is a hexamethylene group, and-(A ³ -O)-at both ends thereof is 1 unit of ethylene oxide and 6 units of propylene oxide.

  From the viewpoint of high resolution, cured film peeling performance, and cured film flexibility, it is preferable to include at least one compound represented by the general formula [IV] as an addition polymerizable monomer.

(Wherein R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, A ⁴ represents an alkylene group having 2 to 6 carbon atoms, and n ⁹ is a number satisfying 2 to 40. A ⁴ present may be the same or different, and the repeating structure of — (A ⁴ —O) — may be random or block.)
In the compound represented by the general formula [IV], A ₄ represents —CH (CH ₃ ) CH ₂ —, —CH ₂ CH (CH ₃ ) —, and —CH ₂ CH from the viewpoint of peeling performance and developer dispersibility. It is preferably at least one selected from the group consisting of _2- , and when different alkylene groups are mixed, the repeating structure is preferably a block.

In the compound represented by the general formula [IV], n ₉ is preferably 2 or more from the viewpoints of flexibility and tenting properties of the cured film, and 40 or less from the viewpoints of resolution and plating resistance. Preferably there is.

Specific examples of the unsaturated compound represented by the general formula [IV] include diacrylates in which A ⁴ is an ethylene group and n ⁹ = 9, and dimethacrylates in which A ⁴ is a propylene group and n ⁹ is 7. , a mixture of a ⁴ is a propylene group and an ethylene group, a polyalkylene oxide dimethacrylate repeating ethylene oxide by respective average 3 units at both ends of propylene oxide with an average 12 units are added is preferable.

  From the viewpoint of high resolution, cured film peeling performance, and plating resistance, it is preferable that the addition polymerizable monomer contains at least one compound represented by the general formula [V].

(In the formula, R ⁹ represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms, R ¹⁰ , R ¹¹ and R ¹² each independently represents a hydrogen atom or a methyl group, and A ⁵ represents carbon. N ¹³ is 0 or 1. n ¹⁰ , n ¹¹ and n ¹² are numbers satisfying n ¹⁰ + n ¹¹ + n ¹² = 3 to 60. ⁵ may be the same or different, and the repeating structure of-(O-A ⁵ )-may be random or block.)
In the compound represented by the general formula [V], A ⁵ represents —CH (CH ₃ ) CH ₂ —, —CH ₂ CH (CH ₃ ) —, and —CH ₂ from the viewpoint of peeling performance and developer dispersibility. It is preferably at least one selected from the group consisting of CH ₂ —, and when different alkylene groups are mixed, the repeating structure is preferably a block.

In the compound represented by the general formula [V], n ¹⁰ + n ¹¹ + n ¹² is preferably 3 or more from the viewpoints of flexibility and tenting properties of the cured film, and is 60 or less from the viewpoint of plating resistance. It is preferable. Preferably they are 3 or more and 30 or less, More preferably, they are 3 or more and 12 or less.
Specific examples of the unsaturated compound represented by the general formula [V] include triacrylate obtained by adding an average of 3 units of ethylene oxide to trimethylolpropane, and an average of 3 units of propylene oxide on trimethylolpropane. A triacrylate obtained by adding a total of 6 units of ethylene oxide to trimethylolpropane on average and a triacrylate obtained by adding a total of 9 units of ethylene oxide on average to trimethylolpropane are preferred.

  From the viewpoint of shortening the peeling time of the cured film and dispersibility of the developer in the unexposed area, it is preferable to include at least one compound represented by the general formula [VI] as the addition polymerizable monomer.

(In the formula, R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 15 carbon atoms, R ¹⁴ represents a hydrogen atom or a methyl group, and A ⁶ represents an alkylene group having 2 to ⁶ carbon atoms. , N ¹⁴ is a number satisfying 1 to 30. In the formula, a plurality of A ⁶ may be the same or different from each other, and the repeating structure of — (O—A ⁶ ) — is random or blocked. It may be.)
In the compound represented by the general formula [VI], A ⁶ represents —CH (CH ₃ ) CH ₂ —, —CH ₂ CH (CH ₃ ) —, and —CH ₂ from the viewpoints of peeling performance and developer dispersibility. It is preferably at least one selected from the group consisting of CH ₂ —, and when different alkylene groups are mixed, the repeating structure is preferably a block.

In the compound represented by the general formula [VI], n ¹⁴ is preferably 1 or more from the viewpoint of raw material handling properties, and preferably 30 or less from the viewpoint of plating resistance.
Specific examples of the unsaturated compound represented by the general formula [VI] include 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate, 4-nonylphenyl octaethylene glycol acrylate, 4-nonylphenyl tetraethylene glycol acrylate, 4 -Octylphenylpentapropylene glycol acrylate is preferred.

  In addition, examples other than the compounds represented by the general formulas [II] to [VI] that can be used as addition polymerizable monomers include known compounds having at least one terminal ethylenically unsaturated group.

  More specific examples of addition polymerizable monomers include, for example, 2-hydroxy-3-phenoxypropyl acrylate, a reaction product of a half ester compound of phthalic anhydride and 2-hydroxypropyl acrylate, and propylene oxide, 1,6- Hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, 2,2-bis (4-methacryloxypentaethoxyphenyl) propane, glycerol Acrylate, triacrylate was acrylated trimethylol propane, tetraacrylate glycol obtained by adding an average 4 moles of ethylene oxide to pentaerythritol, and the like polyfunctional (meth) acrylate of isocyanuric acid ester compounds. These may be used alone or in combination of two or more.

  The content of the addition polymerizable monomer in the photosensitive resin composition is preferably in the range of 5 to 75% by mass. This content is preferably 5% by mass or more from the viewpoint of suppressing curing failure and development time delay, while being 75% by mass or less from the viewpoint of suppressing cold flow and delayed peeling of the cured resist. It is preferable. Moreover, the minimum of more preferable content is 15 mass%, and an upper limit is 60 mass%. Furthermore, the minimum with preferable content is 30 and an upper limit is 50 mass%.

<Photopolymerization initiator>
The photopolymerization initiator is a compound that polymerizes a monomer by light. As the photopolymerization initiator, those usually used as photopolymerization initiators for photosensitive resins can be used as appropriate. In particular, hexaarylbisimidazole (hereinafter also referred to as triarylimidazolyl dimer) is preferably used.

Examples of the triarylimidazolyl dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer (hereinafter referred to as “2,2′-bis (2-chlorophenyl) -4,4 ′, 5”). , 5′-tetraphenyl-1,1′-bisimidazole ”), 2,2 ′, 5-tris- (o-chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ′, 5 '-Diphenylimidazolyl dimer, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenylimidazolyl dimer,
2,4,5-tris- (o-chlorophenyl) -diphenylimidazolyl dimer, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxyphenyl) -imidazolyl dimer, 2, 2′-bis- (2-fluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3-difluoromethyl) Phenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,4-difluorophenyl) -4,4 ′, 5 5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer,
2,2′-bis- (2,5-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2, 6-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,4-trifluorophenyl) -4 , 4 ′, 5,5′-tetrakis- (3-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.

  In particular, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer is a photopolymerization initiator having a high effect on resolution or the strength of a cured resist film, and is preferably used. These may be used alone or in combination of two or more. Further, it can be used in combination with the following acridine compounds, pyrazoline compounds and the like.

Among these, an acridine compound or a pyrazoline compound is preferably used as a photopolymerization initiator. Examples of acridine compounds include acridine, 9-phenylacridine, 9- (4-tolyl) acridine, 9- (4-methoxyphenyl) acridine, 9- (4-hydroxyphenyl) acridine, 9-ethylacridine, 9-chloroethyl. Acridine, 9-methoxyacridine, 9-ethoxyacridine,
9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4-n-butylphenyl) acridine, 9- (4-tert -Butylphenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- (4-acetylphenyl) acridine, 9- (4-dimethylaminophenyl) acridine, 9- (4-chlorophenyl) acridine,
9- (4-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 is mentioned. Of these, 9-phenylacridine is preferable.

  Examples of the pyrazoline compound include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -Pyrazolin, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline is preferred.

As photopolymerization initiators other than the above, for example, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloro Quinones such as anthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone,
Aromatic ketones such as benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], and 4,4′-bis (diethylamino) benzophenone, benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethyl Benzoin ethers such as benzoin,
Benzyl dimethyl ketal, benzyl diethyl ketal, combinations of thioxanthones and alkylaminobenzoic acid, 1-phenyl-1,2-propanedione-2-O-benzoinoxime, 1-phenyl-1,2-propanedione-2- ( And oxime esters such as (O-ethoxycarbonyl) oxime.

  Examples of the combination of the above thioxanthones and alkylaminobenzoic acid include, for example, a combination of ethylthioxanthone and ethyl dimethylaminobenzoate, a combination of 2-chlorothioxanthone and ethyl dimethylaminobenzoate, and isopropylthioxanthone and dimethylaminobenzoate. A combination with ethyl acid is mentioned. N-aryl amino acids may also be used. Examples of N-aryl amino acids include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. Among these, N-phenylglycine is particularly preferable.

  Content of the photoinitiator in the photosensitive resin composition is the range of 0.01-30 mass%, A more preferable minimum is 0.05 mass%, Furthermore, a preferable minimum is 0.1 mass%, More preferable The upper limit is 15% by mass, and a more preferable upper limit is 10% by mass. The content of the photopolymerization initiator is 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity at the time of photopolymerization by exposure, and reaches the bottom of the photosensitive resin composition (that is, a portion far from the light source) at the time of photopolymerization. From the viewpoint of sufficiently transmitting light and obtaining good resolution and adhesion, the content is 30% by mass or less.

<Compound represented by the general formula [I]>
The photosensitive resin composition contains one or more compounds represented by the general formula [I].

(In the formula, R ¹ is a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms, A ¹ is an alkylene group having 2 to 10 carbon atoms, n ¹ , n ² , n ³ , Is a number satisfying n ¹ + n ² + n ³ = ^{3 to} 120, and n ⁴ is 0 or 1. In the formula, a plurality of A ^{1 s} may be the same or different, and — (O—A ¹ ) The repeating structure of-may be random or block.)
Here, in the present embodiment, the compound represented by the general formula [I] is used in combination with other components, so that a good balance of developer dispersibility, plating resistance, and resolution can be obtained as a photosensitive resin composition. Although the details of the mechanism to be realized are not detailed, the present inventors infer as follows.

  That is, the plating resistance and resolution are realized by providing the compound represented by the general formula [I] with an alkylene oxide chain advantageous for chemical resistance, and the developer dispersibility is 3 alkylene oxide chains. It is thought that this can be realized by the polarity of the compound represented by the general formula [I].

In the compound represented by the general formula [I], A ¹ is an alkylene group having 2 to 10 carbon atoms. The number of carbon atoms of the alkylene group is preferably 2 or more from the viewpoint of handleability, preferably 10 or less, more preferably 4 or less from the viewpoint of compatibility with other raw materials. Specifically, as the alkylene group, —CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH (CH ₃ ) CH ₂ —, —CH ₂ CH (CH ₃ ) —, —CH ₂ CH ₂ — and the like can be mentioned, among which —CH (CH ₃ ) CH ₂ — or —CH ₂ CH (CH ₃ ) — is preferable.

The repeating units of — (O—A ¹ ) — may be the same or different. When the repeating unit of-(O-A ¹ )-is different, the structure may be random or block. Further, n ¹ , n ² , and n ³ representing the number of repetitions may be integers of 1 or more and 60 or less, and n ¹ + n ² + n ³ is preferably 3 or more and more preferably 9 or more from the viewpoint of storage stability. . Moreover, 120 or less is preferable from a raw material handleability, and 100 or less is still more preferable.

The content of the compound represented by the general formula [I] in the photosensitive resin composition is in the range of 0.01 to 30% by mass, a more preferable lower limit is 0.05% by mass, and a further preferable lower limit is 0.00. 1 mass%, a more preferred upper limit is 15 mass%, and a further preferred upper limit is 10 mass%. The content of the compound represented by the general formula [I] is 0.01% by mass from the viewpoint of the peeling performance of the cured resist.
From the viewpoint of developer dispersibility and resolution of the unexposed film, it is 30% by mass or less.

The molecular weight of the compound represented by the general formula [I] is 30 from the viewpoint of plating resistance.
More than 00 is preferable, and 3500 or more is more preferable. On the other hand, it is preferably 3000 or less from the viewpoint of developer dispersibility.

<Other additives>
The photosensitive resin composition can contain various additives in addition to the components (a) to (d). Specifically, for example, coloring substances such as dyes and pigments are included. Examples of such coloring substances include base green 1 [CAS number (hereinafter the same): 633-03-4], malachite green oxalate [2437-29-8], brilliant green [ 633-03-4], fuchsin [632-99-5], methyl violet [603-47-4], methyl violet 2B [8004-87-3], crystal violet [548-62-9], methyl green [ 82-94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390-60-5], Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], Basic Yellow 2 [2465-27-2] and the like. Of these, basic green 1, malachite green oxalate, and basic blue 7 are preferable, and basic green 1 and basic blue 7 are particularly preferable from the viewpoint of improving hue stability and exposure contrast.

  When the coloring material is contained, the addition amount of the coloring material is preferably 0.001 to 1% by mass based on the total solid content of the photosensitive resin composition. When the addition amount of the coloring substance is 0.001% by mass or more, there is an effect of improving the handleability, and when it is 1% by mass or less, there is an effect of maintaining the storage stability.

  Moreover, you may contain the color former in the photosensitive resin composition so that a visible image can be given by exposure. Examples of such a coloring dye include a leuco dye or a combination of a fluorane dye and a halogen compound.

  For example, as leuco dyes, tris (4-dimethylamino-2-methylphenyl) methane [leucocrystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green], and fluorane dye Is mentioned. Among these, when leuco crystal violet is used, the contrast is good and preferable.

  Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2, 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, chlorinated triazine compounds and the like.

  When these dyes are contained, the content of the dye in the photosensitive resin composition is preferably 0.1 to 10% by mass based on the total solid content of the photosensitive resin composition.

  Furthermore, in order to improve the thermal stability and storage stability of the photosensitive resin composition, at least one compound selected from the group consisting of radical polymerization inhibitors or benzotriazoles and carboxybenzotriazoles is photosensitive. It is preferable to make it contain in a resin composition.

  Examples of such radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2 Examples include '-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine.

  Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, Examples thereof include bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.

  Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, (N, N-dibutylamino) carboxybenzotriazole, N- ( N, N-di-2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-ethylhexyl) amino And ethylene carboxybenzotriazole.

  The total addition amount of the radical polymerization inhibitor, benzotriazoles, and / or carboxybenzotriazoles is preferably 0.001 to 3% by mass based on the total solid content of the photosensitive resin composition, and more preferably the lower limit. Is 0.05% by mass, and a more preferable upper limit is 1% by mass. The total addition amount is preferably 0.001% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and preferably 3% by mass or less from the viewpoint of maintaining sensitivity.

  You may make the photosensitive resin composition contain another plasticizer as needed. Examples of such plasticizers include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, and polyoxyethylene monoethyl. Glyceres and esters such as ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, sorbitan derivatives such as polyoxyethylene sorbitan laurate and polyoxyethylene sorbitan oleate, and phthalates such as diethyl phthalate , O-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, citric acid Propylene glycol with propylene oxide added to both sides of bisphenol A and ethylene oxide to both sides of bisphenol A and triethyl acetylcitrate, tri-n-propyl acetylcitrate and tri-n-butyl acetylcitrate And ethylene glycol.

  The content of the plasticizer in the photosensitive resin composition is preferably 0.1% by mass to 50% by mass, a more preferable lower limit is 1% by mass, and a more preferable upper limit is 30% by mass. This content is preferably 0.1% by mass or more from the viewpoint of suppressing delay in development time and imparting flexibility to the cured film, while being 50% from the viewpoint of suppressing insufficient curing and cold flow. % Or less is preferable.

  You may make the photosensitive resin composition contain other antioxidant as needed. Examples of the antioxidant include triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (monononylphenyl) phosphite, and bis (monononylphenyl) -dinonylphenyl phosphite. For example, fights.

  The content of the antioxidant in the photosensitive resin composition is preferably in the range of 0.01% by mass to 0.8% by mass, and the more preferable lower limit is 0.01% by mass, and the preferable upper limit is 0.3%. % By mass. When this content is 0.01 mass% or more, the effect which is excellent in the hue stability of the photosensitive resin composition expresses favorably, and the sensitivity at the time of exposure of the photosensitive resin composition becomes favorable. On the other hand, when the content is 0.8% by mass or less, since color developability is suppressed, hue stability is improved and adhesion is also improved.

<Photosensitive resin composition preparation solution>
You may use the photosensitive resin composition mentioned above as the photosensitive resin composition formulation liquid formed by adding a solvent to this. Suitable solvents include ketones represented by methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropyl alcohol. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid is 500 to 4000 mPa · sec at 25 ° C.

<Photosensitive resin laminate>
The photosensitive resin laminated body of this Embodiment contains the photosensitive resin composition layer which consists of the photosensitive resin composition mentioned above, and the support layer which supports the said photosensitive resin composition layer. If necessary, the photosensitive resin composition layer may have a protective layer on the surface opposite to the support-forming side.

  The support is preferably a transparent one that transmits light emitted from the exposure light source. Examples of such a support include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film. , A polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. As these films, those stretched as necessary can be used. The haze is preferably 5 or less. The thinner the film, the more advantageous in terms of image forming property and economic efficiency, but a film having a thickness of 10 to 30 μm is preferably used because the strength needs to be maintained.

  Further, an important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support and can be easily peeled with respect to the adhesion with the photosensitive resin layer. For example, a polyethylene film and a polypropylene film can be preferably used as the protective layer. Further, for example, a film having excellent peelability disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 to 100 μm, and more preferably 10 to 50 μm.

  The thickness of the photosensitive resin layer in the photosensitive resin laminate is preferably 5 to 100 μm, more preferably 7 to 60 μm. As the thickness is thinner, the resolution is improved, and as the thickness is thicker, the film strength is improved.

  As a method for producing a photosensitive resin laminate by laminating a support, a photosensitive resin layer, and if necessary, a protective layer, a conventionally known method can be employed.

  For example, the photosensitive resin composition used for forming the photosensitive resin layer is made into the above-mentioned photosensitive resin composition preparation solution, and is first coated on a support using a bar coater or a roll coater and dried. Then, a photosensitive resin layer made of the photosensitive resin composition is laminated on the support. Then, if necessary, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

<Resist pattern formation method>
The resist pattern forming method of the present embodiment includes, for example, a laminating process for forming a photosensitive resin layer on a substrate using the above-described photosensitive resin laminate, an exposure process for exposing the photosensitive resin layer, and the A development step for forming a resist pattern by removing unexposed portions of the exposed photosensitive resin layer with a developer is sequentially included.

  More specifically, for example, in the laminating step, a photosensitive resin layer is first formed on the substrate using a laminator. Specifically, when the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heat-pressed and laminated on the substrate surface with a laminator. Examples of the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and the like. In this case, the photosensitive resin layer may be laminated on only one surface of the substrate surface, or may be laminated on both surfaces as necessary. The heating temperature at this time is generally 40 to 160 ° C. Moreover, the adhesiveness with respect to the board | substrate of the resist pattern obtained by performing this thermocompression bonding twice or more improves. At this time, a two-stage laminator provided with two rolls may be used for pressure bonding, or a laminate of the substrate and the photosensitive resin layer may be repeatedly passed through the roll and pressure bonded.

  Next, in the exposure step, the photosensitive resin composition is exposed to active light using an exposure machine. If necessary, the exposure can be performed after peeling off the support. In the case of exposure through a photomask, the exposure amount is determined by the light source illuminance and the exposure time, and may be measured using a light meter.

  In the exposure step, a maskless exposure method may be used. In maskless exposure, exposure is performed directly on the substrate by a drawing apparatus without using a photomask. As the light source, a semiconductor laser having a wavelength of 350 nm to 410 nm, an ultrahigh pressure mercury lamp, or the like is used. The drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the illuminance of the exposure light source and the moving speed of the substrate.

Next, in the development step, unexposed portions in the exposed photosensitive resin layer are removed with a developer using a developing device. After exposure, if a support is present on the photosensitive resin layer, this is excluded. Subsequently, the unexposed portion is developed and removed using a developer composed of an alkaline aqueous solution to obtain a resist image. As the alkaline aqueous solution, an aqueous solution such as Na ₂ CO ₃ or K ₂ CO ₃ is preferable. These are selected in accordance with the characteristics of the photosensitive resin layer, and an aqueous Na2CO3 solution having a concentration of 0.2% by mass to 2% by mass is generally used. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed. In addition, it is preferable to maintain the temperature of the developing solution in a development process at a constant temperature in the range of 20 to 40 ° C.

  Although a resist pattern is obtained by the above-mentioned process, depending on the case, the heating process of 100 to 300 degreeC can also be performed further. By carrying out this heating step, chemical resistance can be further improved. For heating, a heating furnace such as hot air, infrared rays, or far infrared rays can be used.

  By applying such a resist pattern forming method, a conductor pattern, a printed wiring board, a lead frame, a substrate having an uneven pattern, a semiconductor package, and the like can be manufactured.

<Conductor pattern>
As a method for producing a conductor pattern, for example, using the above-described photosensitive resin laminate, a laminating step of forming a photosensitive resin layer on a substrate that is a metal plate or a metal film insulating plate, An exposure process for exposure, a development process for forming a resist pattern by removing a non-exposed portion of the exposed photosensitive resin layer with a developer, and a conductor pattern formation for etching or plating the substrate on which the resist pattern is formed A method comprising steps in order is preferred.

<Printed wiring board>
As a method for producing a printed wiring board, for example, after producing a conductor pattern, the resist pattern is peeled off from the substrate with an aqueous solution having alkalinity stronger than the developer, thereby obtaining a printed wiring board having a desired wiring pattern. it can. In the production of a printed board, a copper-clad laminate or a flexible board is preferably used as the board. There is no particular limitation on the alkaline aqueous solution for stripping (hereinafter also referred to as “stripping solution”), but an aqueous solution of NaOH or KOH having a concentration of 2% by mass to 5% by mass is generally used. A small amount of a water-soluble solvent can be added to the stripping solution. The temperature of the stripping solution in the stripping step is preferably in the range of 40 ° C to 70 ° C.

<Lead frame>
As a lead frame manufacturing method, for example, using a metal plate such as copper, copper alloy, or iron-based alloy as a substrate, a resist pattern is formed by the above-described resist pattern forming method, and the exposed substrate is further etched. And a step of forming a conductor pattern. Then, the peeling process which peels a resist pattern with the method similar to the manufacturing method of the above-mentioned printed wiring board is performed, and a desired lead frame is obtained.

<Substrate having an uneven pattern>
The resist pattern formed by the resist pattern forming method can be used as a protective mask member when processing a substrate by a sandblasting method. Examples of the substrate at this time include glass, a silicon wafer, amorphous silicon, polycrystalline silicon, ceramic, sapphire, and a metal material.

As a method for producing a base material having a concavo-convex pattern, for example, a resist pattern is formed on these substrates by the same method as the resist pattern forming method described above. Thereafter, the substrate is subjected to a sandblasting process in which a blast material is sprayed from the formed resist pattern and cut to a desired depth, and a resist pattern portion remaining on the substrate is removed from the substrate with an alkali stripping solution or the like. The method of manufacturing the base material which has a fine uneven | corrugated pattern on it is mentioned. A known material can be used as the blasting material used in the above-mentioned sandblasting process. For example, fine particles having a particle size of about 2 μm to 100 μm such as SiC, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO, glass, stainless steel, etc. are used. It is done.

<Semiconductor package>
As a method for manufacturing a semiconductor package, for example, using a wafer on which a large-scale integrated circuit (LSI) has been formed as a substrate and forming a resist pattern thereon by the above-described resist pattern forming method, the following steps are performed. Through this process, a semiconductor package can be manufactured. First, a step of forming a conductor pattern by performing columnar plating such as copper or solder on the opening exposed by development is performed. Thereafter, a peeling process for peeling the resist pattern by the same method as the above-described method for manufacturing a printed wiring board is performed, and further, a thin metal layer other than the columnar plating is removed by etching. A semiconductor package is obtained.

  Further, the above-described photosensitive resin composition can be used for the manufacture of printed wiring boards, the manufacture of lead frames for mounting IC chips, the manufacture of metal foils such as the manufacture of metal masks, ball grid arrays (BGA), or chip size packages. Manufacturing of packages such as (CSP), manufacturing of tape substrates such as chip-on-film (COF) or tape automated bonding (TAB), manufacturing of semiconductor bumps, flat panel displays such as ITO electrodes or address electrodes, electromagnetic shielding It can be used for the manufacture of partition walls.

  The various parameters described above are measured according to the measurement methods in the examples described later unless otherwise specified.

  Next, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples unless it exceeds the gist. Each physical property was measured by the following method.

(1) Weight average molecular weight, molecular weight distribution It measured with the gel permeation chromatography (GPC) system by JASCO Corporation using the calibration curve of standard polystyrene (Shodex STANDARD SM-105 by Showa Denko KK). Details of the measurement conditions are as follows.
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

(2) Evaluation of developer dispersibility 0.16 m ² of the photosensitive resin layer prepared by the above method was dissolved in 200 ml of a 1% by mass Na ₂ CO ₃ aqueous solution and stirred with a mixer device for 1 minute. The liquid was collected, placed in a 200 ml standard bottle and allowed to stand for 3 days, and aggregates generated in the liquid were collected by suction filtration. The aggregates were dried and then weighed, and the results were ranked as follows.
A: Aggregate is 50 mg or less.
○: Aggregate exceeds 50 mg and 100 mg or less.
X: Aggregate exceeds 100 mg.

(3) Evaluation of resolution Using a 1.2 mm thick copper clad laminate on which 35 μm rolled copper foil is laminated, jet scrub polishing with a spray pressure of 0.20 MPa (manufactured by Nippon Carlit Co., Ltd., Sacradund R (registered trademark)) # 220) was prepared.
While peeling off the polyethylene film of the photosensitive resin laminate, it was laminated at a roll temperature of 105 ° C. with a hot roll laminator (Asahi Kasei Engineering Co., Ltd., AL-70) on a copper clad laminate that had been leveled and preheated to 60 ° C. . The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.
The substrate for resolution evaluation that had passed 15 minutes after the lamination was exposed and developed with a line pattern in which the width of the exposed area and the unexposed area was 1: 1.
The exposure was performed through a photomask necessary for evaluation on the photosensitive resin layer through the support with an ultrahigh pressure mercury lamp (HMW-801 manufactured by Oak Manufacturing Co., Ltd.) with an exposure amount of 7 steps of a 21-step tablet manufactured by Stofer. .
In the development, after removing the polyethylene terephthalate film, a 1 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. is sprayed for a predetermined time using an alkali developing machine (manufactured by Fuji Kiko Co., Ltd., a dry film developing machine), and photosensitive resin is used. The unexposed part of the layer was dissolved and removed in a time twice the minimum image time. The minimum development time was defined as the minimum time required for the photosensitive resin layer in the unexposed portion to be completely dissolved.
The minimum mask width in which the cured resist line was normally formed was defined as the resolution value, and the resolution was ranked as follows.
○: The resolution value is 30 μm or less.
X: The value of resolution exceeds 30 μm.

(4) Evaluation of plating resistance A laminate substrate was prepared, exposed and developed in the same manner as in the resolution evaluation.
Furthermore, copper sulfate plating was performed according to the following plating conditions.
<Plating conditions>
Pretreatment: Dipped in an acidic degreaser bath (LP-200: 5%, manufactured by Rohm and Haas, sulfuric acid: 5% aqueous solution) at 40 ° C. for 4 minutes. Thereafter, it was washed with water, soaked in an APS aqueous solution (ammonium persulfate aqueous solution, concentration 200 g / L) at room temperature for 1 minute, washed with water, and soaked in a 10% sulfuric acid aqueous solution for 2 minutes.
Copper sulfate plating: Plating was performed for 50 minutes at a current density of 5.0 A / dm 2 with the following plating solution composition.
<Composition of copper sulfate plating solution>
Pure water: 58. 9%
Copper sulfate conch (Meltex): 30%
Concentrated sulfuric acid: 10%
Concentrated hydrochloric acid: 0. 1%
Copper cream 125 (Meltex): 1%
The copper sulfate plating line of L / S = 50/50 μm after the cured resist was peeled was observed with an optical microscope and ranked as follows. The cured resist was peeled off by dipping in a 3% by mass aqueous sodium hydroxide solution heated to 50 ° C. on the evaluation substrate after development.
A: Secondary copper plating is hardly seen.
○: Although secondary copper plating is observed, the width is 5 μm or less on one side of the line.
X: Boring width of secondary copper plating exceeds 5 μm on one side of the line.

[Examples 1 to 13 and Comparative Examples 1 to 4]
A photosensitive resin composition solution prepared by blending the compounds shown in Table 1 at the composition ratio shown in Table 2 (unit: parts by mass), further adding MEK as a solvent and sufficiently stirring and mixing, is 16 μm as a support. The surface of a thick polyethylene terephthalate film (manufactured by Teijin DuPont Films, Inc., GR-16) was uniformly applied using a bar coater, and dried in a dryer at 95 ° C. for 4 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 40 μm. In addition, in the composition shown in Table 2, the mass parts of B-1, B-2, and B-3 are solid content.

Next, a 19 μm thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-18) was bonded as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate. .
Using the obtained photosensitive resin laminate, the developer dispersibility, resolution, and plating resistance of the photosensitive resin composition were evaluated. The evaluation results are shown in Tables 2 and 3.

  The above-mentioned photosensitive resin composition, etc. are used for the manufacture of printed wiring boards, the manufacture of lead frames for mounting IC chips, the precision processing of metal foils such as the manufacture of metal masks, the manufacture of packages such as BGA or CSP, COF or TAB, etc. It can be used for the production of tape substrates, semiconductor bumps, ITO or address electrodes, and flat panel display partitions such as electromagnetic wave shields.

Claims (12)

(A) Alkali-soluble polymer 20 to 90% by mass,
(B) 5 to 75% by mass of an addition polymerizable monomer having at least one polymerizable ethylenically unsaturated bond in the molecule;
(C) 0.01-30% by mass of a photopolymerization initiator, and (d) 0.01-30% by mass of a compound represented by the following general formula [I],
The photosensitive resin composition characterized by including.

(In the formula, R ¹ is a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms, A ¹ is an alkylene group having 2 to 10 carbon atoms, n ¹ , n ² , n ³ , Is a number satisfying n ¹ + n ² + n ³ = ^{3 to} 120, and n ⁴ is 0 or 1. In the formula, a plurality of A ^{1 s} may be the same or different, and — (O—A ¹ ) The repeating structure of-may be random or block.) The photosensitive resin composition according to claim 1, wherein the addition polymerizable monomer contains at least one compound selected from the group consisting of compounds represented by the following general formulas [II] to [V].

(In the formula, R ² and R ³ each independently represent a hydrogen atom or a methyl group, A ² represents an alkylene group having 2 to 6 carbon atoms, and n ⁵ and n ⁶ represent n ⁵ + n ⁶ = 2 to 40. (In the formula, a plurality of A ² may be the same or different, and the repeating structure of — (A ² —O) — may be random or block.)

(Wherein R ⁴ represents an alkylene group, R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, A ³ represents an alkylene group having 2 to 6 carbon atoms, and n ⁷ and n ⁸ represent n ⁷ + n ⁸ = 2 to 40. In the formula, a plurality of A ^{3 s} may be the same or different, and the repeating structure of — (A ³ —O) — may be random. It may be a block.)

(Wherein R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, A ⁴ represents an alkylene group having 2 to 6 carbon atoms, and n ⁹ is a number satisfying 2 to 40. A ⁴ present may be the same or different, and the repeating structure of — (A ⁴ —O) — may be random or block.)

(In the formula, R ⁹ represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms, R ¹⁰ , R ¹¹ and R ¹² each independently represents a hydrogen atom or a methyl group, and A ⁵ represents carbon. N ¹³ is 0 or 1. n ¹⁰ , n ¹¹ and n ¹² are numbers satisfying n ¹⁰ + n ¹¹ + n ¹² = 3 to 60. ⁵ may be the same or different, and the repeating structure of-(O-A ⁵ )-may be random or block.) The photosensitive resin composition of Claim 1 or 2 in which the said addition polymerizable monomer contains the compound represented by the following general formula [VI].

(In the formula, R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 15 carbon atoms, R ¹⁴ represents a hydrogen atom or a methyl group, and A ⁶ represents an alkylene group having 2 to ⁶ carbon atoms. , N ¹⁴ is a number satisfying 1 to 30. In the formula, a plurality of A ⁶ may be the same or different from each other, and the repeating structure of — (O—A ⁶ ) — is random or blocked. It may be.)   The photosensitive resin composition of any one of Claims 1-3 in which the said alkali-soluble polymer contains a styrene-type monomer structure.   The photosensitive resin composition of any one of Claims 1-4 in which the said photoinitiator contains 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer.   The photosensitive resin laminated body containing the photosensitive resin composition layer which consists of the photosensitive resin composition in any one of Claims 1-5, and the support layer which supports the said photosensitive resin composition layer.   The process of laminating | stacking the photosensitive resin laminated body of Claim 6 on a board | substrate, the exposure process of exposing the photosensitive resin layer contained in the said photosensitive resin laminated body, The unexposed part in the photosensitive resin layer after the said exposure A resist pattern forming method comprising: a developing step of removing a resist with a developing solution to form a resist pattern.   The resist pattern forming method according to claim 7, wherein the exposure step is a step of performing exposure by direct drawing of a drawing pattern. A method for forming a conductor pattern using the method for forming a resist pattern according to claim 7 or 8,
The said board | substrate is a metal plate or a metal-film insulation board, The formation method of a conductor pattern including the process of etching or plating the part which is not coat | covered with the resist pattern of the said board | substrate surface. A method for producing a printed wiring board using the method for forming a resist pattern according to claim 7 or 8,
The substrate is a copper-clad laminate or a flexible substrate, and includes a step of etching or plating a portion of the substrate surface not covered with the resist pattern, and a step of peeling the resist pattern after the etching or plating step. Manufacturing method of printed wiring board. A lead frame manufacturing method using the resist pattern forming method according to claim 7 or 8,
A method for manufacturing a lead frame, comprising: an etching step of etching a portion of the substrate surface that is not covered with a resist pattern; and a step of peeling the resist pattern after the etching step. A method of manufacturing a semiconductor package using the resist pattern forming method according to claim 7 or 8,
The substrate is a wafer on which an LSI is formed, and includes a plating step of plating a portion of the substrate surface not covered with the resist pattern, and a step of peeling the resist pattern after the plating step. Production method.