JP4931533B2 - Photosensitive resin composition and laminate thereof - Google Patents

Description

  The present invention relates to a photosensitive resin composition and use thereof, and more specifically, a photosensitive resin laminate suitable for manufacturing a conductive pattern such as a printed wiring board, a flexible substrate, and a lead frame, and a method of forming a resist pattern using the same. The present invention relates to a conductor pattern manufacturing method, a printed wiring board manufacturing method, a lead frame manufacturing method, and a semiconductor package manufacturing method.

For electronic devices such as personal computers and mobile phones, printed wiring boards and the like are used for mounting components and semiconductors. A so-called dry film resist (hereinafter abbreviated as DFR) composed of a support, a photosensitive resin layer, and a protective layer has been conventionally used as a resist for manufacturing printed wiring boards and the like. The DFR is generally prepared by laminating a photosensitive resin layer on a support and further laminating a protective layer on the photosensitive resin layer.
As the photosensitive resin layer used here, an alkali developing type using a weak alkaline aqueous solution as a developing solution is generally used.
To create a printed wiring board using DFR, first peel off the protective layer, and then laminate the DFR on a permanent circuit creation board such as a copper-clad laminate or flexible board using a laminator, etc. Exposure is performed through a film or the like. Next, if necessary, the support is peeled off, and the photosensitive resin layer in the unexposed portion is dissolved or dispersed and removed with a developing solution to form a resist pattern on the substrate.

  After forming the resist pattern, the process for forming a circuit is roughly divided into two methods. The first method is a method in which after removing a copper surface such as a copper-clad laminate not covered with a resist pattern by etching, the resist pattern portion is removed with an alkaline aqueous solution stronger than the developer. In this case, for simplicity of the process, a method (tenting method) in which a through hole (through hole) is covered with a cured film and then etched is frequently used. The second method is to remove the resist pattern portion after performing plating treatment of copper, solder, nickel, tin, etc. on the above copper surface, and further etch the copper surface of the copper-clad laminate, etc. that appeared ( Plating method). In any case, cupric chloride, ferric chloride, a copper ammonia complex solution or the like is used for etching.

  Responding to the recent miniaturization of printed wiring boards mounted on personal computers and the like, high resolution and adhesion of resists are required. High resolution is generally achieved by improving the crosslinking density of the photosensitive resin composition. However, when the crosslinking density is increased, the cured resist film becomes hard and brittle. When using the tenting method, it is required that the cured film does not break through the tenting process (tenting property), but the problem is that the tented property deteriorates due to the hardened film. To do. In addition, if the cured film is broken by pressure such as spraying in the development or etching process, the copper line is broken, causing a defect. Therefore, a resist having high resolution and good cured film flexibility and tenting properties is required.

In addition, if the etchant resistance is weak in the etching process, the etchant may permeate from the bottom surface of the resist, which may cause defects due to rattling of the copper circuit or flow of the resist line.
The step of dissolving or dispersing and removing the photosensitive resin layer in the unexposed portion with a developer after exposure is called a development step. Not all of the DFR components dissolve in the developer, and each time the development process is repeated, insoluble components with poor developer dispersibility increase and aggregates (scum) are generated. Aggregates re-adhere on the substrate, causing a short circuit failure in the tenting and etching methods, and may clog the developing tank piping. Therefore, for the purpose of reducing aggregates, as a photopolymerizable unsaturated compound, an attempt to use an alkylphenol type monofunctional monomer with good developer dispersibility (Patent Document 1) or an attempt to use a phenoxy type monofunctional monomer (Patent) There are references 2), but none of them was satisfactory.

Patent Document 3 discloses a photosensitive resin composition using a binder resin containing benzyl methacrylate as a copolymer component, and Patent Document 4 discloses a photosensitive resin composition using an acridine compound. However, these have excellent developer dispersion stability, do not generate agglomerates, exhibit high resolution, and exhibit various effects such as good cured film flexibility, tenting properties, and good etching solution resistance. The request for a photosensitive resin composition excellent in balance has not been sufficiently met.
Therefore, a photosensitive resin composition having excellent developer dispersion stability in the development process, generating no agglomerates, expressing high resolution, good cured film flexibility, tenting properties, and good etching solution resistance. It has been sought.

JP 2001-174986 A JP 2001-305730 A JP 2005-121790 A Japanese Patent Laid-Open No. 2002-323761

  The present invention is a photosensitive resin composition having good post-development resolution, excellent developer dispersion stability, not generating aggregates, excellent cured film flexibility, tenting properties, and good etchant resistance, An object of the present invention is to provide a photosensitive resin laminate having a photosensitive resin layer composed of the composition, and to provide a resist pattern forming method and a conductor pattern manufacturing method using the laminate. .

As a result of studying to solve the above problems, by using a specific photosensitive resin composition, the developer dispersion stability is excellent, no aggregates are generated, resolution and adhesion are good, tenting properties, and good. It has been found that it has a good etching solution resistance and can form a good conductor pattern, and has led to the present invention.
That is, this invention is invention of the manufacturing method of the following photosensitive resin compositions, photosensitive resin laminated bodies, a resist pattern formation method, and a conductor pattern.
(1) (a) A binder having a carboxyl group content of 100 to 600 in terms of acid equivalent, 10 to 90% by mass of benzyl (meth) acrylate as a copolymer component, and a weight average molecular weight of 5,000 to 500,000. Resin for use: 10 to 90% by mass, (b) Photopolymerizable unsaturated compound: 5 to 70% by mass, (c) 0.1 to 20 of a compound represented by the following general formula (I) as a photopolymerization initiator mass%, a compound of feeling light resin composition you containing 0.01 to 10 wt%, represented by the following formula (II),
A photosensitive resin composition comprising at least one compound represented by the following general formulas (V) and (VI) as the photopolymerizable unsaturated compound (b) .
(In the formula, A is hydrogen, an aryl group, a heterocyclic group, a linear or branched alkyl group having 1 to 6 carbon atoms or an alkoxy group, and NR ₂ (where R is a hydrogen atom or having 1 to 6 carbon atoms) Represents a substituent selected from the group consisting of an alkyl group).
Wherein B is an aryl group, a heterocyclic group, a linear or branched alkyl group having 1 to 6 carbon atoms, and NR ₂ (R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). And b represents an integer of 0 to 5. In the formula, X represents a halogen atom.
(In the formula, R ₅ and R ₆ are H or CH ₃ , and these may be the same or different. R ₃ and R ₄ are an ethylene group or a propylene group, and are the same respectively. In this case, the repeating unit of — (R ₃ —O) — and — (R ₄ —O) — may be a block structure or a random structure, m5, m6, n5. , And n6 are each independently 0 or a positive integer, and the sum of these is 2 to 40.)
(In the formula, R ₉ and R ₁₀ are H or CH ₃ , and these may be the same or different. R ₇ and R ₈ are an ethylene group or a propylene group, and are the same respectively. In this case, the repeating unit of- (R ₇ -O) -and- (R ₈ -O)-may be a block structure or a random structure.m7, m8, n7 , And n8 are each independently 0 or a positive integer, and the sum of these is 2 to 40.)
(2) (c) As a photopolymerization initiator, a compound represented by the following general formula (III) is 0.1 to 1
The photosensitive resin composition according to (1), further containing 9.9% by mass.
(In the formula, C, D, and E each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, or a halogen group; c, d, and e each independently represent 1; It is an integer of ~ 5.)
(3) The photosensitive resin composition according to (1) or (2), further comprising 0.1 to 20% by mass of a compound represented by the following general formula (IV).
(R ₁ and R ₂ are ethylene groups or propylene groups, which are different from each other. M1, n1, m2, n2, m3, n3, m4, and n4 are integers of 0 or more, and m1 + n1 + m2 + n2 + m3 + n3 + m4 + n4 is 0 to 0. 40. The repeating structure of — (R ₁ —O) — and — (R ₂ —O) — may be random or block, and F, G, H and I are independent of each other. And hydrogen or a fatty acid acyl group having 1 to 30 carbon atoms.)
( 4 ) A photosensitive resin laminate comprising a photosensitive resin composition layer obtained by laminating the photosensitive resin composition according to any one of (1) to ( 3 ) on a support.
( 5 ) A method for forming a resist pattern, comprising: laminating the photosensitive resin laminate according to ( 4 ) on a substrate, exposing the substrate, and then removing an unexposed portion by development.
( 6 ) A method for producing a conductor pattern comprising a step of etching or plating a substrate on which a resist pattern is formed by the method according to ( 5 ).
( 7 ) A method for producing a printed wiring board, comprising a step of etching or plating a substrate on which a resist pattern is formed by the method according to ( 5 ).
( 8 ) A method for manufacturing a lead frame, comprising a step of etching a substrate on which a resist pattern is formed by the method described in ( 5 ).
( 9 ) A method for manufacturing a semiconductor package, comprising a step of etching or plating a substrate on which a resist pattern has been formed by the method described in ( 5 ).
( 10 ) A method of processing a substrate on which a resist pattern is formed by the method according to ( 5 ) by a sandblasting process.

  According to the present invention, the developer dispersion stability is excellent in the development process, no aggregates are generated, the resolution is good, and the cured film has flexibility, tenting properties, and good etching solution resistance. A photosensitive resin composition suitable for forming a good conductor pattern, and a photosensitive resin laminate having a photosensitive resin layer comprising the composition can be provided. Moreover, the formation method of the resist pattern using this laminated body and the manufacturing method of conductor patterns, such as a printed wiring board which has fine wiring, can be provided.

Hereinafter, the present invention will be specifically described.
The photosensitive resin laminate used in the present invention is a laminated film in which a photosensitive resin layer is sandwiched between a support and a protective layer, or a protective layer is peeled from the laminated film. Sometimes called film, dry film, dry film resist or DFR.
As for content of the carboxyl group contained in (a) resin for binders used for this invention, 100-600 are preferable at an acid equivalent, More preferably, it is 300-450. An acid equivalent means the mass of the linear polymer which has a 1 equivalent carboxyl group in it.
The carboxyl group in the binder resin is necessary to give the photosensitive resin layer developability and releasability with respect to an aqueous alkali solution. The acid equivalent is preferably 100 or more from the viewpoint of development resistance, resolution, and adhesion, and is preferably 600 or less from the viewpoint of developability and peelability.

The weight average molecular weight of the (a) binder resin used in the present invention is preferably 5,000 to 500,000. The weight average molecular weight of the binder resin is preferably 500000 or less from the viewpoint of resolution, and 5000 or more is preferable from the viewpoint of edge fuse. Edge fuse refers to a phenomenon in which when a resist roll is stored, the resist oozes out from the end of the roll, generating chips and causing defects.
In order to better exhibit the effects of the present invention, the weight average molecular weight of the binder resin is more preferably 5,000 to 200,000, still more preferably 5,000 to 100,000. The degree of dispersion (sometimes referred to as molecular weight distribution) is represented by the ratio of the weight average molecular weight to the number average molecular weight of the following formula.
(Dispersity) = (weight average molecular weight) / (number average molecular weight)
The degree of dispersion is about 1 to 6, preferably 1 to 4.

The acid equivalent is measured by a potentiometric titration method using a Hiranuma automatic titration apparatus (COM-555) manufactured by Hiranuma Sangyo Co., Ltd., and using a 0.1 mol / L sodium hydroxide aqueous solution.
The molecular weight is gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK (KF-807, KF-806M, KF -806M, KF-802.5) 4 in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (use of calibration curve by Shodex STANDARD SM-105 Polystyrene manufactured by Showa Denko KK) as weight average molecular weight (polystyrene conversion) Desired.

  The (a) binder resin used in the present invention contains benzyl (meth) acrylate as an essential component from the viewpoint of resolution and aggregation. The benzyl (meth) acrylate of the present invention is a compound in which an aromatic ring is substituted with an alkoxy group having 1 to 6 carbon atoms, halogen, or an alkyl group having 1 to 6 carbon atoms, specifically, ethoxybenzyl (meth) acrylate, Benzyl (meth) acrylates such as methoxybenzyl (meth) acrylate, chlorobenzyl (meth) acrylate, methylbenzyl (meth) acrylate, and ethylbenzyl (meth) acrylate are included. In particular, benzyl (meth) acrylate having no substituent is preferred.

The content of benzyl (meth) acrylate in the binder resin is preferably 10 to 90% by mass. 90 mass% or less is preferable from the viewpoint of developability, and 10 mass% or more is preferable from the viewpoint of aggregation. More preferably, it is 20-85 mass%, More preferably, it is 30-80 mass%, Most preferably, it is 40-80 mass%.
In the present invention, (meth) acrylate represents acrylate and methacrylate.
(A) Resin for binder used in the present invention is at least one of the following first monomers from the following two types of monomers in addition to benzyl (meth) acrylate, and further if necessary It can be obtained by copolymerizing the following second monomer.

The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. Examples include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester, and the like.
The second monomer is a non-acidic compound having one polymerizable unsaturated group in the molecule. The compound is selected so as to maintain various properties such as developability of the photosensitive resin layer, resistance in etching and plating processes, and flexibility of the cured film. Examples of the compound include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 -Hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate, (meth) acrylonitrile, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, cresyl ( Aryl (meth) acrylates such as meth) acrylate and naphthyl (meth) acrylate, vinyl compounds having a phenyl group (for example, styrene), and the like can be used.

The first monomer (a) is preferably contained in the binder resin in an amount of 5 to 50% by mass, and the second monomer is preferably contained in an amount of 0 to 85% by mass.
(A) Binder resin used in the present invention is a mixture of benzyl (meth) acrylate and the first monomer and / or the second monomer, a solvent such as acetone, methyl ethyl ketone, or isopropanol. It is preferable to carry out the synthesis by adding an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to the solution diluted with, 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.

The ratio of the resin for binder (a) used in the present invention to the total of the photosensitive resin composition is in the range of 10 to 90% by mass, preferably 30 to 70% by mass. The resist pattern formed by exposure and development is preferably 10% by mass or more and 90% by mass or less from the viewpoint that the resist pattern has sufficient resistance as a resist, for example, tenting, etching, and various plating processes. Moreover, you may contain resin for binders other than the resin for binders which contains the said benzyl (meth) acrylate as a copolymerization component in the photosensitive resin composition of this invention.
Among the photopolymerizable unsaturated compounds (b) used in the present invention, the photopolymerizable unsaturated compounds represented by the following general formulas (V) and (VI) will be described.

(In the formula, R ₅ and R ₆ are H or CH ₃ , and these may be the same or different. R ₃ and R ₄ are an ethylene group or a propylene group, and are the same respectively. In this case, the repeating unit of — (R ₃ —O) — and — (R ₄ —O) — may be a block structure or a random structure, m5, m6, n5. , And n6 are each independently 0 or a positive integer, and the sum of these is 2 to 40.)

(In the formula, R ₉ and R ₁₀ are H or CH ₃ , and these may be the same or different. R ₇ and R ₈ are an ethylene group or a propylene group, and each is the same. In this case, the repeating units of — (R ₇ —O) — and — (R ₈ —O) — may have a block structure or a random structure, m7, m8, n7, And n8 are each independently 0 or a positive integer, and the sum of these is 2 to 40.)

In the compound represented by the general formula (V), the lower limit of m5 + m6 + n5 + n6 is preferably 2 or more, and the upper limit is preferably 40 or less. More preferably, it is 15-40, More preferably, it is 20-40.
In the compound represented by the general formula (VI), the lower limit of m7 + m8 + n7 + n8 is preferably 2 or more, and the upper limit is preferably 40 or less.
In the compounds represented by the general formulas (V) and (VI), when these values are less than 2, the flexibility and tenting properties of the cured film deteriorate, and when these values exceed 40, the effect on the resolution is obtained. Not enough.

  Specific examples of the general formula (V) include polyethylene glycol dimethacrylate (NK ester BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.) in which an average of 2 moles of ethylene oxide is added to both ends of bisphenol A. Polyethylene glycol dimethacrylate (NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.) with an average of 5 moles of ethylene oxide added to both ends of bisphenol A, and an average of 6 moles of ethylene oxide to both ends of bisphenol A Polyalkylene glycol dimethacrylate with an average of 2 moles of propylene oxide added to both ends of bisphenol A and polyalkylene glycol dimethacrylate with an average of 15 moles of ethylene oxide added to both ends of bisphenol A Polyalkylene glycol dimethacrylate with an average of 15 moles of ethylene oxide and an average of 1 mole of propylene oxide, and polyalkylene with an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide on both ends of bisphenol A, respectively. Examples include glycol dimethacrylate and polyalkylene glycol dimethacrylate in which an average of 15 mol of ethylene oxide and an average of 3 mol of propylene oxide are added to both ends of bisphenol A, respectively.

  Specific examples of the general formula (VI) include 2,2-bis {(4-acryloxypolyethoxy) cyclohexyl} propane or 2,2-bis {(4-methacryloxypolyethoxy) cyclohexyl}. The ethoxy group of propane is monoethoxy, diethoxy, triethoxy, tetraethoxy, pentaethoxy, hexaethoxy, heptaethoxy, octaethoxy, nonaethoxy, decaethoxy, undecaethoxy, dodecaethoxy, tridecaethoxy, tetradecaethoxy, pentadecaethoxy. And alkylene groups also include mixtures of ethylene and propylene groups such as 2,2-bis {(4-acryloxypolyalkyleneoxy) cyclohexyl} propane or 2,2-bis {(4-methacryloxypoly). Alkyleneoxy) Alkyleneoxy groups hexyl} propane adducts of adducts and random structure of the block structure of the adduct and tetraethoxy and tetrapropyloxy adducts and random structure of the block structure of octa ethoxy and di propyloxy and the like. Among these, 2,2-bis {(4-methacryloxypentaethoxy) cyclohexyl} propane is most preferable.

  (B) In addition to the compound groups represented by the general formulas (V) and (VI), the photopolymerizable unsaturated compounds shown below can be used in combination. For example, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) ) Propane di (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropylene trimethylolpropane tri (meth) acrylate, polyoxyethylenetrimethylolpropane tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, β-hydroxypropyl-β ′-(acryloyloxy) propyl phthalate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyalkylene glycol (meta ) Acrylate, polypropylene glycol mono (meth) acrylate, polyalkylene glycol di (meth) acrylate obtained by adding ethylene oxide to both ends of polypropylene glycol to which propylene oxide is added.

Moreover, a urethane compound is also mentioned. Examples of the urethane compound include a diisocyanate compound such as hexamethylene diisocyanate, tolylene diisocyanate, or 2,2,4-trimethylhexamethylene diisocyanate, and a compound having a hydroxyl group and a (meth) acryl group in one molecule (2- And urethane compounds obtained by reaction with hydroxypropyl acrylate, oligopropylene glycol monomethacrylate, etc.). Specifically, there is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (Nippon Yushi Co., Ltd., Blenmer PP1000).
(B) As for the ratio with respect to the sum total of the photosensitive resin composition of a photopolymerizable unsaturated compound, 5 mass% or more is preferable from a sensitivity viewpoint, and 70 mass% or less is preferable from a viewpoint of an edge fuse. More preferably, it is 10-60 mass%, More preferably, it is 15-55 mass%.

(B) Each of the photopolymerizable unsaturated compounds represented by the general formulas (V) and (VI) is preferably in the range of 5 to 60% by mass, more preferably, relative to the photosensitive resin composition. It is the range of 7-35 mass%, More preferably, it is the range of 10-30 mass%.
Moreover, (b) The ratio of the sum total of the photopolymerizable unsaturated compound represented by the said general formula (V) and (VI) with respect to the sum total of the photosensitive resin composition is the range of 5-70 mass%. From the viewpoint of resolution, it is 5% by mass or more, and from the viewpoint of flexibility of the resist pattern, it is 70% by mass or less. More preferably, it is 10-40 mass%.
The acridine represented by the following general formula (I) will be described as the photopolymerization initiator (c) used in the present invention.

(In the formula, A is hydrogen, an aryl group, a heterocyclic group, a linear or branched alkyl group having 1 to 6 carbon atoms or an alkoxy group, and NR ₂ (where R is a hydrogen atom or having 1 to 6 carbon atoms) Represents a substituent selected from the group consisting of an alkyl group).

  The ratio with respect to the sum total of the photosensitive resin composition of the compound represented by the said general formula (I) is 0.1-20 mass%. If this ratio is less than 0.1% by mass, sufficient sensitivity cannot be obtained. On the other hand, when the ratio exceeds 20% by mass, fogging due to diffraction of light passing through the photomask at the time of exposure tends to occur, and as a result, resolution is deteriorated. Examples of the compound represented by the general formula (I) include 9-phenylacridine, 9-methylacridine, 9-ethylacridine, 9-propylacridine, 9- (4-pyridyl) -acridine and the like. Of these, 9-phenylacridine is particularly preferable.

It is a preferred embodiment from the viewpoint of high resolution that the (c) photopolymerization initiator used in the present invention contains a 2,4,5-triarylimidazole dimer represented by the following general formula (III). is there.
(Wherein, C, D, and E each independently represent any of hydrogen, an alkyl group, an alkoxy group, and a halogen group, and c, d, and e are each independently an integer of 1-5.)

  In the compound represented by the general formula (III), the covalent bond for bonding two lophine groups is 1,1′-, 1,2′-, 1,4′-, 2,2′-, Although it is in the 2,4′- or 4,4′-position, a compound in the 1,2′-position is preferred. Examples of the 2,4,5-triarylimidazole dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis- ( m-methoxyphenyl) imidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, etc., and in particular, 2- (o-chlorophenyl) -4,5-diphenylimidazole. Dimers are preferred.

As for the ratio with respect to the sum total of the photosensitive resin composition of the compound represented by the said general formula (III), 0.1-19.9 mass% is preferable. 0.3 mass% or more and 10 mass% or less are preferable, and 0.5 mass% or more and 8 mass% or less are more preferable.
In the present invention, the ratio of the photopolymerization initiator (c) to the total of the photosensitive resin composition is 0.1 to 20% by mass. If this ratio is less than 0.1% by mass, sufficient sensitivity cannot be obtained. On the other hand, when the ratio exceeds 20% by mass, fogging due to diffraction of light passing through the photomask at the time of exposure tends to occur, and as a result, resolution is deteriorated.
In addition, the compounds represented by the general formulas (I) and (III) can be used in combination, and can also be used in combination with other photopolymerization initiators. Here, the photopolymerization initiator is a compound that is activated by various actinic rays such as ultraviolet rays and starts polymerization.

Other photopolymerization initiators include, for example, quinones such as 2-ethylanthraquinone and 2-tert-butylanthraquinone, aromatic ketones such as benzophenone, benzoin ethers such as benzoin, benzoin methyl ether and benzoin ethyl ether, Examples include benzyl dimethyl ketal and benzyl diethyl ketal.
Further, for example, there are combinations of thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and tertiary amine compounds such as dimethylaminobenzoic acid alkyl ester compounds.

Further, there are oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime. In addition, 1-phenyl-3- (4-tert-butyl-styryl) -5- (p-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- Pyrazolines represented by (4-tert-butylstyryl) -5- (4-tert-butylphenyl) -pyrazoline can also be used.
Further, N-aryl-α-amino acid compounds can also be used, and among these, N-phenylglycine is particularly preferable.

Use of the compound represented by the following general formula (IV) in the photosensitive resin composition of the present invention is useful for improving the dispersion stability of the developer and suppressing the generation of aggregates.
(R ₁ and R ₂ are ethylene groups or propylene groups, which are different from each other. M1, n1, m2, n2, m3, n3, m4, and n4 are integers of 0 or more, and m1 + n1 + m2 + n2 + m3 + n3 + m4 + n4 is 0-40. The repeating structure of (R ₁ —O) — and — (R ₂ —O) — may be random or block, and F, G, H, and I are each independently hydrogen or carbon number 1 ˜30 fatty acid acyl groups.)

If m1 + n1 + m2 + n2 + m3 + n3 + m4 + n4 in the general formula (IV) exceeds 40, sufficient sensitivity and adhesion cannot be obtained. In addition, the fatty acid acyl group having 1 to 30 carbon atoms includes a saturated fatty acid acyl group having 1 to 30 carbon atoms and an unsaturated fatty acid acyl group having 1 to 30 carbon atoms. Examples of the saturated fatty acid acyl group having 1 to 30 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, lauroyl group, myristyl group, palmityl group, stearyl group and the like. Examples of the unsaturated fatty acid acyl group having 1 to 30 carbon atoms include an acryl group, a propinoyl group, a methacryl group, and an oleoyl group.
Although the following compounds are mentioned as a compound shown by the said general formula (IV), It is not limited to this.

  Examples of the ester type include sorbitan laurate [F: lauroyl group, G = H = I: hydrogen, m1 + n1 + m2 + n2 + m3 + n3 + m4 + n4 = 0 (example: New Emuls Co., Ltd., Newcor (trademark) 20)], sorbitan stearate [ F: stearyl group, G = H = I: hydrogen, m1 + n1 + m2 + n2 + m3 + n3 + m4 + n4 = 0 (example: Sanyo Chemical Industries, Ionet (trademark) S-60C)], sorbitan oleate [F: oleoyl group, G = H = I: hydrogen, m1 + n1 + m2 + n2 + m3 + n3 + m4 + n4 = 0 (Example: Sanyo Chemical Industries, Ionet (trademark) S-80C)], sorbitan palmitate [F: palmityl group, G = H = I: hydrogen, m1 + n1 + m2 + n3 + n3 + n3 + n3 + n4 + Example: Toho Chemical Industry Co., Ltd. Sorbon (trademark) S-40)], sorbitan coconut oil fatty acid ester [F: acyl group of coconut oil fatty acid (where coconut oil is a fat obtained from the palm meat of the palm family, and the fatty acid is lauric acid) And G = H = I: hydrogen, m1 + n1 + m2 + n2 + m3 + n3 + m4 + n4 = 0 (eg, Sanyo Chemical Industries, Ionette) S-20)], sorbitan trioleate [F = G = I: oleoyl group, H: hydrogen, m1 + n1 + m2 + n2 + m3 + n3 + m4 + n4 = 0 (eg, Sanyo Chemical Industries, Ionet (trademark) S-85, or Japanese emulsifier ( Co., Ltd., New Coal (trademark) 3-80)], and mixtures thereof.

As a composite type of sorbitan and oxyethylene chain, polyoxyethylene sorbitan laurate [F: lauroyl group, G = H = I: hydrogen, m1 + m2 + m3 + m4 = 20, n1 + n2 + n3 + n4 = 0, R1: ethylene group (example: Japanese emulsifier (stock) , Newcor (trademark) 25)], polyoxyethylene sorbitan stearate [F: stearyl group, G = H = I: hydrogen, m1 + m2 + m3 + m4 = 20, n1 + n2 + n3 + n4 = 0, R1: ethylene group (example: Sanyo Chemical Industries) Manufactured by Ionette (trademark) T-60C)], polyoxyethylene sorbitan oleate [F: oleyl group, G = H = I: hydrogen, m1 + m2 + m3 + m4 = 8 or 20, n1 + n2 + n3 + n4 = 0, R1: ethylene group ( Example: New Coal (trademark) manufactured by Nippon Emulsifier Co., Ltd. 82 or 85)], polyoxyethylene sorbitan palmitate [F: palmityl group, G = H = I: hydrogen, m1 + m2 + m3 + m4 = 20, n1 + n2 + n3 + n4 = 0, R1: ethylene group (example: manufactured by Toho Chemical Co., Ltd., sorbon) (Trademark) T-40)], polyoxyethylene sorbitan trioleate [F = G = I: oleoyl group, H: hydrogen, m1 + m2 + m3 + m4 = 20, n1 + n2 + n3 + n4 = 0, R1: ethylene group (example: Nippon Emulsifier Co., Ltd.) Manufactured by Newcor (trademark) 3-85)], polyoxyethylene sorbitan coconut oil fatty acid ester [F: acyl group of coconut oil fatty acid, G = H = I: hydrogen, m1 + m2 + m3 + m4 = 20, n1 + n2 + n3 + n4 = 0, R1: ethylene Group (eg, Sanyo Chemical Industries, Ionet T-2) C)], polyoxyalkylene sorbitan fatty acid ester [F: acyl group of mixed fatty acid (oleic acid: 66%, stearic acid: 2%, saturated and unsaturated fatty acid with 20 carbon atoms: 18%, saturated with 16 carbon atoms and Unsaturated fatty acids: 7%, saturated and unsaturated fatty acids with more than 20 carbon atoms: 7%), G = H = I: hydrogen, m1 + n1 + m2 + n2 + m3 + n3 + m4 + n4 = 30, (m1 + m2 + m3 + m4) / (n1 + n2 + n3 + n4) = 2/1, R1: ethylene group , R2: propylene group (example: Nippon Emulsifier Co., Ltd., New Coal (trademark) 95-FJ)] and mixtures thereof.

  These compounds represented by the general formula (IV) may be used alone or in combination of two or more. The compound represented by the general formula (IV) is preferably contained in an amount of 0.1 to 20% by mass with respect to the total of the photosensitive resin composition. If it is less than 0.1% by mass, it is difficult to obtain a sufficient effect of reducing aggregates during development. If it exceeds 20% by mass, photopolymerization does not proceed efficiently, and image forming properties such as sensitivity and resolution by development are not possible. Is inferior. Preferably it is 0.1-10 mass%, More preferably, it is 0.5-5 mass%.

The compound represented by the following general formula (II) used in the present invention will be described.
Wherein B is an aryl group, a heterocyclic group, a linear or branched alkyl group having 1 to 6 carbon atoms, and NR ₂ (R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). And b represents an integer of 0 to 5. In the formula, X represents a halogen atom.

As for the ratio with respect to the whole photosensitive resin composition of the compound represented by the said general formula (II), 0.01-10 mass% is preferable. It is preferably 0.01% by mass or more from the viewpoint of recognizing sufficient colorability (coloring property), 10% by mass or less from the viewpoint of maintaining the contrast between the exposed part and the unexposed part and maintaining storage stability.
Specific examples of the compound represented by the general formula (II) include tribromomethylphenylsulfone, trichloromethylphenylsulfone, tribromomethyl- (4-methylphenyl) sulfone and the like. In particular, tribromomethylphenylsulfone is preferable.

The photosensitive resin composition of the present invention may contain a coloring substance such as a dye or a pigment, or a coloring dye that develops color when irradiated with light. Examples of the coloring substance used include fuchsin, phthalocyanine green, auramin base, paramadienta, crystal violet, methyl orange, nile blue 2B, malachite green (Eizen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), Victoria blue ( Hodogaya Chemical Co., Ltd. Eisen (registered trademark) VICTORIA PURE BLUE), Basic Blue 20, Diamond Green (Hodogaya Chemical Co., Ltd. Eisen (registered trademark) DIAMOND GREEN GH) and the like.
Examples of the coloring dye include a combination of a leuco dye or a fluorane dye and a halogen compound. Examples of the leuco dye include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet], tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green], and the like.

Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, carbon tetrabromide, tris (2,3-dibromopropyl) phosphate, Examples include trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, and triazine compounds. Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine and 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine.
Among such coloring dyes, a combination of tribromomethylphenylsulfone and a leuco dye or a combination of a triazine compound and a leuco dye is useful.
The amount of the coloring substance and the color former is preferably 0.01 to 10% by mass in the photosensitive resin composition. It is preferably 0.01% by mass or more from the viewpoint of recognizing sufficient colorability (coloring property), 10% by mass or less from the viewpoint of maintaining the contrast between the exposed part and the unexposed part and maintaining storage stability.

  In order to improve the thermal stability and storage stability of the photosensitive resin composition in the present invention, it is preferable that the photosensitive resin composition contains the following additives. Examples of such additives include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2′- Examples include methylene bis (4-ethyl-6-tert-butylphenol), 2,2′-methylene bis (4-methyl-6-tert-butylphenol), diphenylnitrosamine and the like. Further, as stabilizers, a compound in which propylene oxide is further added to both sides of polypropylene glycol in which an average of 1 mol of propylene oxide is added to both sides of bisphenol A, benzotriazole, carboxybenzotriazole, 1- (2-dialkylamino) carboxybenzo There is triazole, pentaerythritol 3,5-di-t-butyl-4-hydroxyphenylpropionic acid tetraester.

The total amount of the additives is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass. From the viewpoint of imparting storage stability to the photosensitive resin composition, 0.01 mass% or more is preferable, and from the viewpoint of maintaining sensitivity, 3 mass% or less is more preferable.
Furthermore, you may make the photosensitive resin composition of this invention contain a plasticizer as needed. Examples of such plasticizers include phthalates such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl citrate tri- Examples thereof include n-propyl, tri-n-butyl acetylcitrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, and the like.

As a quantity of a plasticizer, it is preferable to contain 5-50 mass% in the photosensitive resin composition, More preferably, it is 5-30 mass%. 5 mass% or more is preferable from a viewpoint of suppressing the delay of image development time or providing a softness | flexibility to a cured film, and 50 mass% or less is preferable from a viewpoint of suppressing insufficient hardening and cold flow.
The photosensitive resin laminate of the present invention is produced by laminating the photosensitive resin composition on a support to form a photosensitive resin layer.
As the support, a transparent base film that normally transmits actinic rays is used. Examples of such a base film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate having a thickness of about 10 μm to 100 μm. However, polyethylene terephthalate having usually adequate flexibility and strength is preferably used. The film thickness is preferably 10 μm or more in order to make it difficult to generate wrinkles during lamination and to prevent damage to the support. In order to obtain sufficient resolution, the film thickness is preferably 30 μm or less. The haze is preferably 5 or less. Although the film thickness of the photosensitive resin layer of this invention changes with uses, it is 5 micrometers or more and 100 micrometers or less normally. More preferably, they are 5 micrometers or more and 50 micrometers or less.

In the photosensitive resin laminate of the present invention, a protective layer is formed on the surface of the photosensitive resin layer opposite to the support of the photosensitive resin layer as necessary. It is necessary for the protective layer that the adhesive strength between the photosensitive resin layer and the protective layer is smaller than the adhesive strength between the photosensitive resin layer and the support. The layer can be easily peeled off.
The protective layer is a film for protecting the photosensitive resin layer of the present invention. Examples of such a film include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate having a thickness of about 10 to 100 μm. A film or a polypropylene film is preferably used. The thickness of the protective layer is preferably 10 μm or more and 50 μm or less.

Next, the manufacturing method of the photosensitive resin laminated body of this invention is demonstrated.
A conventionally known method can be adopted as a method of forming a photosensitive resin laminate by sequentially laminating a support, a photosensitive resin layer, and a protective layer.
For example, the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent that dissolves them to make a uniform solution, and is first coated on a support using a bar coater or roll coater and dried. A photosensitive resin layer made of a photosensitive resin composition is laminated thereon.
Next, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.
In the present invention, examples of the substrate include a copper-clad laminate, a flexible substrate, and a metal plate.

<Method for manufacturing printed wiring board>
Next, an example of a method for producing a printed wiring board using the photosensitive resin laminate of the present invention will be described.
A printed wiring board is manufactured through the following steps.
(1) Lamination process The process of making it adhere | attach using hot roll laminators on board | substrates, such as a copper clad laminated board and a flexible substrate, peeling off the protective layer of the photosensitive resin laminated body.
(2) Exposure process The process of sticking the mask film which has a desired wiring pattern on a support body, and performing exposure using an actinic light source.
Or the process of drawing and exposing a wiring pattern directly on a resist without a mask film.

(3) Development process The process which melt | dissolves or disperses the unexposed part of the photosensitive resin layer using an alkali developing solution after peeling a support body, and forms a resist pattern on a substrate.
(4) Etching process or plating process An etching solution is sprayed on the formed resist pattern to etch a copper surface not covered with the resist pattern, or copper, solder, nickel, and copper are not covered with the resist pattern. A step of performing a plating process such as tin.
(5) Stripping step The step of removing the resist pattern from the substrate using an alkaline stripping solution.

Examples of the active light source used in the (2) exposure step include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, and a xenon lamp. In order to obtain a finer resist pattern, it is more preferable to use a parallel light source. When it is desired to reduce the influence of dust or foreign matter as much as possible, exposure (proximity exposure) may be performed in a state where the photomask is floated from several tens of micrometers to several hundreds of micrometers from the support. If necessary, the support may be peeled off and exposed to active light through a photomask. The exposure amount is determined from the light source illuminance and the exposure time. You may measure using a photometer.
In the exposure process, a maskless exposure method may be used. In maskless exposure, exposure is performed by directly drawing on a substrate without using a photomask. As the light source, a semiconductor laser having a wavelength of 350 to 410 nm, an ultrahigh pressure mercury lamp, or the like is used. The drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the light source illuminance and the moving speed of the substrate.

Examples of the alkaline developer used in the above (3) development step include aqueous solutions of sodium carbonate, potassium carbonate and the like. These alkaline aqueous solutions are selected in accordance with the characteristics of the photosensitive resin layer, but generally an aqueous sodium carbonate solution of 0.5% by mass to 3% by mass is used.
The (4) etching step is performed by a method suitable for the DFR used, such as acidic etching or alkaline etching.
As the alkali stripping solution used in the above (5) stripping step, an alkaline aqueous solution that is generally stronger than the alkaline aqueous solution used in the development, for example, 1% by weight to 5% by weight of sodium hydroxide, potassium hydroxide An aqueous solution may be mentioned.
When a plating process such as a semi-additive method is provided, the copper surface that appears under the resist pattern may be etched after the resist pattern is removed.

<Lead frame manufacturing method>
The lead frame manufacturing method of the present invention is performed through the following steps following the above-described resist pattern forming method using a metal plate of copper, copper alloy, iron-based alloy or the like as a substrate.
First, a conductive pattern is formed by etching the substrate exposed by development.
Thereafter, the resist pattern is peeled off by a method similar to the method for manufacturing a printed wiring board described above to obtain a desired lead frame.

<Semiconductor package manufacturing method>
The method for producing a semiconductor package of the present invention is performed by performing the following steps following the above-described resist pattern forming method using a wafer on which a circuit as an LSI has been formed as a substrate.
A conductor pattern is formed by performing columnar plating such as copper or solder on the opening exposed by development.
Thereafter, the resist pattern is peeled off by the same method as the above-described printed wiring board manufacturing method,
Furthermore, a desired semiconductor package is obtained by removing the thin metal layer at portions other than the columnar plating by etching.

<Processing method by sandblasting>
When processing the substrate by the sandblasting method using the photosensitive resin laminate of the present invention as a dry film resist, the photosensitive resin laminate is laminated on the substrate in the same manner as described above, Exposure and development are performed. Further, a blasting material is sprayed from the formed resist pattern to be cut to a desired depth, and a resin part remaining on the base material is removed from the base material with an alkaline stripping solution, etc. A fine pattern can be processed. The blasting material used for the above-mentioned sandblasting process may be a known material, for example, fine particles of about 2 to 100 μm such as SiC, SiO ₂ , Al ₂ O ₃ , CaCO ₃ , ZrO, glass, stainless steel and the like.
Hereinafter, examples of embodiments of the present invention will be described in more detail by way of examples.

Below, the preparation method of the sample for evaluation of an Example and a comparative example, the evaluation method about the obtained sample, and an evaluation result are shown.
1. Production of Evaluation Samples The photosensitive resin laminates in Examples and Comparative Examples were produced as follows.
<Preparation of photosensitive resin laminate>
Prepare the compounds shown in Table 1, thoroughly stir and mix the photosensitive resin composition of the composition ratio shown in Table 2, and apply uniformly to the surface of a 20 μm thick polyethylene terephthalate film as a support using a bar coater, The photosensitive resin layer was formed by drying for 4 minutes in a dryer at 95 ° C. The thickness of the photosensitive resin layer was 40 μm.
In the composition shown in Table 1, MEK represents methyl ethyl ketone, and the mass parts of P-1 to P-5 in Table 2 are values including MEK.
Next, a 25 μm thick polyethylene film was laminated 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.

<Board surface preparation>
Etching solution resistance, resolution, adhesion, and tenting property evaluation use a 1.6 mm thick copper clad laminate with 35 μm rolled copper foil laminated on the surface, wet buffol polishing (manufactured by 3M Co., Ltd., Scotch Bright) (Registered trademark) HD # 600, twice).
<Laminate>
While peeling 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 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.

<Exposure>
A mask film necessary for evaluation is placed on a polyethylene terephthalate film, which is a support, on a photosensitive resin layer, and a 21-step tablet made by Stöffer is 7 steps by an ultra-high pressure mercury lamp (OMW Seisakusho, HMW-201KB). The exposure amount was as follows. When this exposure method is selected, it is shown in Table 2 as a “photomask”.
Or, using a direct drawing type exposure apparatus (manufactured by Hitachi Via Mechanics Co., Ltd., DI exposure machine DE-1AH, light source: GaN blue-violet diode, main wavelength 407 ± 3 nm) without using a mask film, a 21-step tablet made by Stöffer Was exposed at an exposure amount of 7 steps. When this exposure method is selected, it is shown in Table 2 as “direct drawing”.

<Development>
After the polyethylene terephthalate film is peeled off, a 1 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. is sprayed for a predetermined time using an alkali developing machine (produced by Fuji Kiko Co., Ltd., a dry film developing machine), and an unexposed portion of the photosensitive resin layer Was dissolved and removed in a time twice the minimum image time. At this time, the minimum time required for completely dissolving the photosensitive resin layer in the unexposed portion was defined as the minimum development time.
<Etching>
The developed substrate was etched with a salt copper etching apparatus (manufactured by Tokyo Chemical Industry Co., Ltd.) at 3 mol / l hydrochloric acid, 250 g / l cupric chloride at 50 ° C. for 1.3 times the minimum etching time. At this time, the time when the copper foil on the substrate was completely dissolved and removed was defined as the minimum etching time.

<Resist stripping>
The cured resist was peeled off by spraying a 3% by mass aqueous sodium hydroxide solution heated to 50 ° C. onto the evaluation substrate after development.
2. Evaluation Method (1) Resolution Evaluation A substrate for resolution evaluation that had passed 15 minutes after lamination was exposed with a line pattern in which the width of the exposed area and the unexposed area was 1: 1. Development was performed with a development time twice as long as the minimum development time, and the minimum mask width in which a cured resist line was normally formed was defined as a resolution value, and the resolution was ranked as follows.
A: Resolution value of 30 μm or less ○: Resolution value of more than 30 μm, 35 μm or less Δ: Resolution value of more than 35 μm, 40 μm or less ×: Resolution value of more than 40 μm

(2) Evaluation of cohesion A photosensitive layer (resist layer) having a thickness of 40 μm and an area of 0.16 m ^{2 in} the photosensitive resin laminate is dissolved in 200 ml of a 1% by mass Na ₂ CO ₃ aqueous solution, and a circulation spray device is used. The spray pressure was 0.1 MPa for 3 hours. Thereafter, the developer was allowed to stand for 1 day, and the generation of aggregates was observed. When a large amount of agglomerates are generated, powdery or oily substances are observed at the bottom and side surfaces of the spray device. In addition, aggregates may float in the developer. The composition having good developer cohesiveness does not generate these aggregates at all, or even if they are generated, they can be easily washed away from the spray device by washing with water. The state of occurrence of aggregates was ranked by visual observation as follows.
A: No agglomerates are generated. O: There is no agglomerates at the bottom or side of the spray device, but a very small amount of agglomerates that can be visually confirmed are observed in the developer, but they are easily washed away when washed with water.
(Triangle | delta): The aggregate is floating in the bottom part or side surface part of a spray apparatus, and a developing solution.
Even if it is washed with water, everything cannot be washed away.
X: Aggregates are observed in the entire spray apparatus and the aggregates are floating in the developer.
It is impossible to wash everything away with water, and most of it remains.

(3) Cured film flexibility evaluation DFR having a thickness of 40 μm was laminated on a copper-clad laminate, and the entire surface was exposed with HMW-201KB with a 7-step exposure of a 21-step tablet made by Stöffer. After the polyethylene terephthalate as a support was peeled off, a 1 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed at twice the minimum development time to obtain a cured image. Eleven cuts with a width of 1 mm were made at right angles to the obtained cured image, and cellotape (registered trademark) was peeled off. At this time, the following ranking was performed according to the degree of peeling of the cured resist by peeling of the cello tape (registered trademark). That the resist is easily peeled means that the cured film has poor flexibility.
A: The cured resist is not peeled off at all.
○: A part of the cured resist is peeled off.
Δ: The cured resist is almost peeled off.
X: The cured resist peels off when the cut is made.

(4) Tenting property A through-hole with a radius of 6 mm exists at equal intervals (1008 holes). A photosensitive resin is laminated on a tenting evaluation substrate, and a 21-step tablet made by Stöffer becomes 7 steps by HMW-201KB. The entire film was exposed with an exposure amount, developed with a development time twice as long as the minimum development time, and further washed with water at a spray pressure of 0.3 MPa in a water-washing tank, and the film tear rate was measured.
The following ranking was performed according to the film tear rate.
○: Film tear rate is less than 1%.
(Triangle | delta): The film tear rate is less than 1 to 5%.
X: Film tear rate is 5% or more.

(5) Etching property evaluation A substrate for resolution evaluation which has passed 15 minutes after lamination is subjected to 7 steps of 21 step tablet made by Stofer using HMW-201KB through a line pattern mask in which the width of the exposed part and the unexposed part is 1: 1. It exposed with the exposure amount used as a step. Developed with a development time twice as long as the minimum development time, etched at 1.3 mol of hydrochloric acid 3 mol / l, cupric chloride 250 g / l, 1.3 times the minimum etching time at 50 ° C, and then stripped the resist to remove the copper line A substrate with a formed thereon was obtained. The copper line top width of the portion having a mask line width of 100 μm was measured. At this time, the closer the copper line top width is to 100 μm, the more the etching solution does not penetrate under the resist, and the etching solution resistance is considered to be stronger. The following ranking was performed according to the width of the copper line.
○: 80 μm or more.
Δ: 70 μm or more and less than 80 μm.
X: Less than 70 micrometers.
3. The evaluation results of Examples , Reference Examples and Comparative Examples are shown in Table 2.

From Table 2, it can be seen that Examples 1 to 7 satisfy the requirements of this application, so that the resolution is good, almost no aggregates are generated, and the cured film flexibility, tenting property, and etching solution resistance are good. On the other hand, since Comparative Example 1 does not contain the compound represented by the general formula (I) as (c) photopolymerization initiator, these effects are inferior. Comparative Example 2 is (a) benzyl (meth) acrylate as a copolymerization component. Since a binder resin containing benzene is not used, these effects are also inferior, and Comparative Examples 3 to 5 are (a) a binder resin containing benzyl (meth) acrylate as a copolymerization component, and (c) a photopolymerization initiator. Since the compound represented by the general formula (I) is not contained, these effects are inferior.
The effect of the present invention is exhibited only when both (a) a binder resin containing benzyl (meth) acrylate as a copolymerization component and (c) a compound represented by formula (I) as a photopolymerization initiator are contained. I understand that.

  According to the present invention, it is suitable as an etching resist or a plating resist in the fields of production of printed wiring boards, flexible wiring boards, lead frames, semiconductor packages and the like, and precision metal processing.

Claims (10)

(A) Resin for binders having a carboxyl group content of 100 to 600 in terms of acid equivalent, 10 to 90% by mass of benzyl (meth) acrylate as a copolymerization component, and a weight average molecular weight of 5,000 to 500,000: 10 to 90% by mass, (b) photopolymerizable unsaturated compound: 5 to 70% by mass, (c) 0.1 to 20% by mass of a compound represented by the following general formula (I) as a photopolymerization initiator, a compound sensitive optical resin composition you containing 0.01 to 10 wt%, represented by the following formula (II),
A photosensitive resin composition comprising at least one compound represented by the following general formulas (V) and (VI) as the photopolymerizable unsaturated compound (b) .
(In the formula, A is hydrogen, an aryl group, a heterocyclic group, a linear or branched alkyl group having 1 to 6 carbon atoms or an alkoxy group, and NR ₂ (where R is a hydrogen atom or having 1 to 6 carbon atoms) Represents a substituent selected from the group consisting of an alkyl group).
Wherein B is an aryl group, a heterocyclic group, a linear or branched alkyl group having 1 to 6 carbon atoms, and NR ₂ (R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). And b represents an integer of 0 to 5. In the formula, X represents a halogen atom.
(In the formula, R ₅ and R ₆ are H or CH ₃ , and these may be the same or different. R ₃ and R ₄ are an ethylene group or a propylene group, and are the same respectively. In this case, the repeating unit of — (R ₃ —O) — and — (R ₄ —O) — may be a block structure or a random structure, m5, m6, n5. , And n6 are each independently 0 or a positive integer, and the sum of these is 2 to 40.)
(In the formula, R ₉ and R ₁₀ are H or CH ₃ , and these may be the same or different. R ₇ and R ₈ are an ethylene group or a propylene group, and are the same respectively. In this case, the repeating unit of- (R ₇ -O) -and- (R ₈ -O)-may be a block structure or a random structure.m7, m8, n7 , And n8 are each independently 0 or a positive integer, and the sum of these is 2 to 40.) (C) 0.1 to 19.9 mass% of compounds represented by the following general formula (III) are further contained as a photoinitiator, The photosensitive resin composition of Claim 1 characterized by the above-mentioned.
(In the formula, C, D, and E each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, or a halogen group; c, d, and e each independently represent 1; It is an integer of ~ 5.) The photosensitive resin composition according to claim 1 or 2, further comprising 0.1 to 20% by mass of a compound represented by the following general formula (IV).
(R ₁ and R ₂ are ethylene groups or propylene groups, which are different from each other. M1, n1, m2, n2, m3, n3, m4, and n4 are integers of 0 or more, and m1 + n1 + m2 + n2 + m3 + n3 + m4 + n4 is 0 to 0. 40. The repeating structure of — (R ₁ —O) — and — (R ₂ —O) — may be random or block, and F, G, H and I are independent of each other. And hydrogen or a fatty acid acyl group having 1 to 30 carbon atoms.) It has the photosensitive resin composition layer formed by laminating | stacking the photosensitive resin composition of any one of Claims 1-3 on a support body, The photosensitive resin laminated body characterized by the above-mentioned. A method for forming a resist pattern, comprising: laminating a photosensitive resin laminate according to claim 4 on a substrate, exposing the laminate, and then removing an unexposed portion by development. A method for producing a conductor pattern, comprising a step of etching or plating a substrate on which a resist pattern is formed by the method according to claim 5 . A method for producing a printed wiring board, comprising a step of etching or plating a substrate on which a resist pattern is formed by the method according to claim 5 . A method for manufacturing a lead frame, comprising a step of etching a substrate on which a resist pattern is formed by the method according to claim 5 . A method for manufacturing a semiconductor package, comprising a step of etching or plating a substrate on which a resist pattern is formed by the method according to claim 5 . A method for processing a substrate on which a resist pattern is formed by the method according to claim 5 by a sandblasting process.