JP4761923B2 - Photosensitive resin composition and laminate - Google Patents

Description

  The present invention relates to a photosensitive resin composition and its use, and in particular, a printed wiring board, a flexible substrate, a lead frame substrate, a COF (chip on film) substrate, a semiconductor package substrate, a liquid crystal transparent electrode, and a liquid crystal TFT. The present invention relates to a photosensitive resin laminate suitable for manufacturing conductor patterns such as wiring and electrodes for plasma display panel (PDP), and a method for forming a resist pattern using the same.

  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. In this case, the cured film is required to have resistance to an etchant and that the cured film does not break through the tenting process (tenting property). 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). For etching, cupric chloride, ferric chloride, a copper ammonia complex solution, or the like is used.

  The step of dissolving or dispersing and removing the photosensitive resin layer in the unexposed portion with the above developer is called a developing 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 and cause short-circuit defects in the tenting and etching methods. For the purpose of reducing aggregates, (b) Attempts to use alkylphenol type monofunctional monomers with good developer dispersibility as photopolymerizable unsaturated compounds (Patent Document 1) and attempts to use phenoxy type monofunctional monomers ( There is Patent Document 2), but none of them is satisfactory.

Further, in response to the recent miniaturization of printed wiring boards mounted on personal computers and the like, high resolution and adhesion of resists are required (Patent Document 3). High resolution is generally achieved by increasing the crosslink density of the photosensitive resin composition. However, when the crosslink density is increased, the cured resist film becomes hard and brittle, and the cured film lacks in the transport process. May occur. In particular, in the case of a thin film having a photosensitive layer of about 10 μm or less, it is easily fogged due to the influence of halation of the transmitted light on the surface of the base material, causing a short circuit. Further, due to halation, a development residue called sushi may be generated on the bottom surface of the cured film. When the soot is generated, depending on the size of the soot, there may be a problem that rattling occurs in the copper circuit during the etching process.

  Therefore, high resolution is developed for the production of COF substrates that require fine resolution and thin film resolution of printed wiring boards, and the developer dispersion stability in the development process is excellent, and aggregates are not generated. There has been a demand for a photosensitive resin composition having a very small width after development and having good etching characteristics.

JP 2001-174986 A JP 2001-305730 A JP 2001-159817 A

  The present invention relates to a photosensitive resin composition that exhibits high resolution and high adhesion, has a resist shape with extremely small sushi after development, and has good etching characteristics, and a photosensitive resin comprising the composition. It aims at providing the photosensitive resin laminated body which has a conductive resin layer, and the formation method of the resist pattern using this laminated body, and the manufacturing method of a conductor pattern.

As a result of studying to solve the above-mentioned problems, by using a specific photosensitive resin composition, high resolution and high adhesiveness are expressed, and the sushi after development has very small and good etching characteristics, The present inventors have found that a good conductor pattern can be formed, and have reached the present invention.
That is, the present invention is the invention of the following photosensitive resin composition, photosensitive resin laminate, resist pattern forming method, and conductor pattern manufacturing method.
(1) (a) Carboxylic acid or acid anhydride having a carboxyl group content of 100 to 600 in terms of acid equivalent and a weight average molecular weight of 5,000 to 500,000 and having at least one polymerizable unsaturated group in the molecule. A resin for a binder obtained by copolymerizing at least one monomer each from a monomer of the above and a monomer of a non-acidic compound having one polymerizable unsaturated group in the molecule, (b ) photopolymerizable unsaturated compounds, containing one or more compounds, selected from the group of (c) a photopolymerization initiator, and (d) the following general formula (I) and (II), (b) a photopolymerization 1 or more types of compounds chosen from the group of the following general formula (III), (IV), and (V) as a photosensitive unsaturated compound, The photosensitive resin composition characterized by the above-mentioned.

（式中、Ｒ₁、Ｒ₂、Ｒ₃及びＲ₄はＨ、炭素数１〜１０のアルキル基、アリール基またはＣＨ（ＣＨ_３）ＣＯＯＣ_８Ｈ_１７であり、これらは同一であっても相違してもよい。）

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are H, an alkyl group having 1 to 10 carbon atoms, an aryl group or CH (CH ₃ ) COOC ₈ H ₁₇ , which may be the same or different. You may do it.)

（式中、Ｑ ₁ 及びＱ ₂ は、ＨまたはＣＨ ₃ であり、これらは同一であっても相違してもよい。また、Ａ及びＢは、エチレン基又はプロピレン基であり、それぞれ同一であっても異なっていてもよく、異なっている場合、−(Ａ−Ｏ)−及び−(Ｂ−Ｏ)−の繰り返し単位は、ブロック構造でもランダム構造でもよい。ｎ ₁ 、ｎ ₂ 、ｎ ₃ 、及びｎ ₄ は、それぞれ独立に０又は正の整数であり、これらの合計は、２〜４０である。） (Wherein R ₅ , R ₆ , R ₇ and R ₈ are H, an alkyl group having 1 to 10 carbon atoms, an aryl group or CH (CH ₃ ) COOC ₈ H ₁₇ , which are the same or different. May be.)

(In the formula, Q ₁ and Q ₂ are H or CH ₃ , and these may be the same or different. A and B are an ethylene group or a propylene group, and each is the same. In the case where they are different, the repeating unit of-(A-O)-and-(B-O)-may be a block structure or a random structure: n ₁ , n ₂ , n ₃ , And n ₄ are each independently 0 or a positive integer, and the sum of these is 2 to 40.)

(Where Q _Three And Q _Four Is H or CH _Three These may be the same or different. D and E are ethylene groups or propylene groups, which may be the same or different, and in the case where they are different,-(D-O)-and-(E-O)-repeating units. May have a block structure or a random structure. n _Five , N ₆ , N ₇ And n ₈ Are each independently 0 or a positive integer, and the sum of these is 2 to 40. )

(Where Q _Five And Q ₆ Is H or CH _Three These may be the same or different and m ₁ , M ₂ And m _Three Are each independently an integer of 3 to 20. )

(2) (a) Resin for binder: 20-90% by mass, (b) Photopolymerizable unsaturated compound: 3-70% by mass, (c) Photopolymerization initiator: 0.1-20% by mass, and ( d) the above general formula (I) and
1 or more compounds selected from the group of (II): 0.05-5 mass%, The photosensitive resin composition as described in (1) characterized by the above-mentioned.
(3) (a) The binder resin contains benzyl (meth) acrylate as a monomer of the non-acidic compound having one polymerizable unsaturated group in the molecule (1) or (2) The photosensitive resin composition.

(4) (c) The photosensitive resin composition as described in any one of (1) to (3), which contains a compound represented by the following general formula (VI) as a photopolymerization initiator: .

(In the formula, X, Y, and Z each independently represent any of hydrogen, an alkyl group, an alkoxy group, and a halogen group, and p, q, and r are each independently an integer of 1 to 5).

(5) A photosensitive resin laminate comprising the photosensitive resin composition according to any one of (1) to (4) on a support.
(6) Formation of a resist pattern characterized in that the photosensitive resin laminate according to (5) is laminated on the surface of a metal plate or metal-coated insulating plate, exposed and developed to remove unexposed portions. Method.
(7) A method for producing a conductor pattern, comprising etching or plating a substrate on which a resist pattern is formed by the method described in (6).

  According to the present invention, the resist has a resist shape that exhibits high resolution and high adhesion, and has extremely small sushi after development, and has good etching characteristics. PROBLEM TO BE SOLVED: To provide a photosensitive resin composition that has excellent developer dispersion stability and does not generate aggregates, and a photosensitive resin laminate having a photosensitive resin layer made of the composition, and a resist using the laminate A pattern forming method and a conductor pattern manufacturing method 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 layer and a protective layer, or a protective layer is peeled off from the laminated film. Sometimes called film, dry film (resist) or DFR.
The amount of the carboxyl group contained in the binder resin (a) used in the present invention is preferably 100 to 600, more preferably 300 to 450, in terms of acid equivalent. An acid equivalent means the mass of resin for binders which has 1 equivalent of a carboxyl group in it.
The carboxyl group in the binder resin is necessary to give the photosensitive resin layer developability and releasability to an alkaline aqueous 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.

(A) Carboxylic acid or acid having a carboxyl group content of 100 to 600 in terms of acid equivalent and a weight average molecular weight of 5,000 to 500,000 having at least one polymerizable unsaturated group in the molecule. Resin for binders (hereinafter simply referred to as binder) obtained by copolymerizing one or more monomers from monomers of anhydrides and non-acidic monomers having one polymerizable unsaturated group in the molecule. The weight average molecular weight of the resin is also preferably 5000 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. In order to further exhibit the effects of the present invention, the weight average molecular weight of the binder resin is more preferably 5,000 to 200,000, and further 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 was measured by 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,
It is calculated | required as a weight average molecular weight (polystyrene conversion) by moving bed solvent: tetrahydrofuran and the use of a calibration curve by a polystyrene standard sample.

The (a) binder resin used in the present invention is obtained by copolymerizing one or more monomers from the following two types of monomers.
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-hydroxypropyl (meth) acrylate, (meth) acrylonitrile, benzyl (meth) acrylate, methoxybenzyl (meth) acrylate, chlorobenzyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydro Aryl (meth) acrylates such as furfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, cresyl (meth) acrylate, naphthyl (meth) acrylate, vinyl compounds having a phenyl group (for example, Styrene) and the like can be used. In particular, benzyl (meth) acrylate is preferable from the viewpoint of resolution and developer aggregation. In the above description, for example, description with benzyl (meth) acrylate indicates benzyl methacrylate or benzyl acrylate.

  The resin for binder (a) used in the present invention is a solution obtained by diluting a mixture of the first monomer and the second monomer with 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 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 (a) binder resin used in the present invention to the entire photosensitive resin composition is preferably in the range of 20 to 90 mass%, more preferably 30 to 70 mass%. The resist pattern formed by exposure and development is preferably 20% by mass or more and 90% by mass or less from the viewpoint that resist characteristics, for example, sufficient resistance in tenting, etching, and various plating processes.
The use of one or more compounds selected from the group of the following general formulas (I) and (II) used in the present invention as the photosensitive resin composition is an essential component from the viewpoint of high resolution. . In particular, a thin photosensitive layer having a thickness of 10 μm or less tends to be fogged (not exhibiting high resolution) because it is easily affected by halation during exposure. The above-described problems can be overcome by using one or more compounds consisting of the following general formulas (I) and (II) as the photosensitive resin composition.

（式中、Ｒ₁、Ｒ₂、Ｒ₃、及びＲ₄はＨ、炭素数１〜１０のアルキル基、アリール基またはＣＨ（ＣＨ_３）ＣＯＯＣ_８Ｈ_１７であり、これらは同一であっても相違してもよい）

Wherein R ₁ , R ₂ , R ₃ , and R ₄ are H, an alkyl group having 1 to 10 carbon atoms, an aryl group, or CH (CH ₃ ) COOC ₈ H ₁₇ , which may be the same May be different)

（式中、Ｒ_５、Ｒ_６、Ｒ_７、及びＲ_８はＨ、炭素数１〜１０のアルキル基、アリール基またはＣＨ（ＣＨ_３）ＣＯＯＣ_８Ｈ_１７でありこれらは同一であっても相違してもよい）一般式（Ｉ）の化合物としては、例えば、Ｒ₁、Ｒ₂、Ｒ₃、及びＲ₄がノルマルブチル基であるチバ・スペシャルティ・ケミカルズ（株）製のＴＩＮＵＶＩＮ（登録商標）４６０や、Ｒ_1、Ｒ₃、Ｒ₄がＣＨ（ＣＨ_３）ＣＯＯＣ_８Ｈ_１７でありＲ₂がＨであるチバ・スペシャルティ・ケミカルズ（株）製のＣＧＬ７７７ＭＰＡ Ｄがある。

(Wherein R ₅ , R _6, R ₇ , and R ₈ are H, an alkyl group having 1 to 10 carbon atoms, an aryl group, or CH (CH ₃ ) COOC ₈ H ₁₇ , which may be the same or different. Examples of the compound of the general formula (I) include TINUVIN (registered trademark) manufactured by Ciba Specialty Chemicals Co., Ltd. in which R ₁ , R ₂ , R ₃ , and R ₄ are normal butyl groups. 460, CGL777MPA D manufactured by Ciba Specialty Chemicals Co., Ltd., in which R _1, R ₃ , and R ₄ are CH (CH ₃ ) COOC ₈ H ₁₇ and R ₂ is H.

Examples of the compound of the general formula (II) include Ciba Specialty, wherein R ₅ is CH (CH ₃ ) COOC ₈ H ₁₇ (iso-octyl), R ₆ is H, R ₇ and R ₈ are phenyl groups. There is TINUVIN (registered trademark) 479 manufactured by Chemicals Corporation.
From the viewpoint of resolution, TINUVIN (registered trademark) 460 is more preferable.

In the photosensitive resin composition of the present invention, the ratio of the compound represented by (d) one or more compounds of the general formulas (I) and (II) is 0.05 to 5% by mass. If this proportion is less than 0.05% by mass, the effect on the resolution is not sufficient, and if this proportion exceeds 5% by mass, the resist surface hardening proceeds from the bottom surface, resulting in poor adhesion.
Preferably it is 0.1 mass% or more, More preferably, it is 0.3% or more, Preferably, it is 3 mass% or less, More preferably, it is 2 mass% or less.
As the photopolymerizable unsaturated compound (b) used in the present invention, the following general formulas (III) and (IV
) And (V) will be described. It is a preferred embodiment from the viewpoint of resolution that it contains at least one compound selected from the group of the following general formulas (III), (IV) and (V).

（式中、Ｑ_１及びＱ_２は、ＨまたはＣＨ_３であり、これらは同一であっても相違してもよい。また、Ａ及びＢは、エチレン基又はプロピレン基であり、それぞれ同一であっても異なっていてもよく、異なっている場合、−(Ａ−Ｏ)−及び−(Ｂ−Ｏ)−の繰り返し単位は、ブロック構造でもランダム構造でもよい。ｎ_１、ｎ_２、ｎ_３、及びｎ_４は、それぞれ独立に０又は正の整数であり、これらの合計は、２〜４０である。）

(In the formula, Q ₁ and Q ₂ are H or CH ₃ , and these may be the same or different. A and B are an ethylene group or a propylene group, and each is the same. In the case where they are different, the repeating unit of-(A-O)-and-(B-O)-may be a block structure or a random structure, n ₁ , n ₂ , n ₃ , And n ₄ are each independently 0 or a positive integer, and the sum of these is 2 to 40.)

（式中、Ｑ_３及びＱ_４は、ＨまたはＣＨ_３であり、これらは同一であっても相違してもよい。また、Ｄ及びＥは、エチレン基又はプロピレン基であり、それぞれ同一であっても異なっていてもよく、異なっている場合、−(Ｄ−Ｏ)−及び−(Ｅ−Ｏ)−の繰り返し単位は、ブロック構造でもランダム構造でもよい。ｎ_５、ｎ_６、ｎ_７、及びｎ_８は、それぞれ独立に０又は正の整数であり、これらの合計は、２〜４０である。）

(In the formula, Q ₃ and Q ₄ are H or CH ₃ , and these may be the same or different. D and E are ethylene groups or propylene groups, and each is the same. In the case where they are different, the repeating unit of-(DO)-and-(EO)-may be a block structure or a random structure: n ₅ , n ₆ , n ₇ , And n ₈ are each independently 0 or a positive integer, and the sum of these is 2 to 40.)

（式中、Ｑ_５及びＱ_６はＨ又はＣＨ_３であり、これらは同一であっても相違してもよく、ｍ_１、ｍ_２、ｍ_３は３〜２０の整数である。）

(Wherein, _{Q 5} and _{Q 6} are H or CH _3, they may be different even in the _{same, m 1, m 2, m} 3 is an integer from 3 to 20.)

In the compound represented by the general formula (III), the lower limit of n ₁ + n ₂ + n ₃ + n ₄ is preferably 2 or more, and the upper limit is preferably 40 or less. When n ₁ + n ₂ + n ₃ + n ₄ is less than 2, the flexibility and tenting properties of the cured film are deteriorated. When n ₁ + n ₂ + n ₃ + n ₄ exceeds 40, the effect on the resolution is not sufficient. As a specific example represented by the above general formula (III), 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, respectively. 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 and dimethylphenol of polyalkylene glycol with an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide added to both ends of bisphenol A, respectively. There is an acrylate.

Similarly, in the compound represented by the general formula (IV), the lower limit of n ₅ + n ₆ + n ₇ + n ₈ is preferably 2 or more, and the upper limit is preferably 40 or less. When n ₅ + n ₆ + n ₇ + n ₈ is less than 2, the flexibility and tenting properties of the cured film deteriorate, and when n ₅ + n ₆ + n ₇ + n ₈ exceeds 40, the effect on resolution is not sufficient. Specific examples of the compound represented by the general formula (IV) include polyethylene glycol dimethacrylate in which an average of 5 mol of ethylene oxide is added to both ends of hydrogenated bisphenol A.

In the compound represented by the general formula (V), m ₁ , m ₂ and m ₃ are preferably 3 or more from the viewpoint of the flexibility of the cured film. From the viewpoint of sensitivity due to the concentration of the photoactive site per unit mass, m ₁ , m ₂ and m ₃ are preferably 20 or less. Specific examples of the compound represented by the general formula (V) used in the present invention include, for example, a glycol obtained by adding an average of 3 moles of ethylene oxide to both ends of polypropylene glycol having an average of 12 moles of propylene oxide added. Preferred examples thereof include dimethacrylate of glycol and diglycolate of glycol obtained by adding an average of 7.5 mol of ethylene oxide to both ends of polypropylene glycol to which an average of 18 mol of propylene oxide is added.

(B) In addition to the compound groups represented by the general formulas (III), (IV), and (V), 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) 0-propanepropane (meth) acrylate -Polyoxyethyltrimethylolpropane triacrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether Tertri (meth) acrylate, bisphenol
A-diglycidyl ether terdi (meth) acrylate, β-hydroxypropyl-β ′-(acryloyloxy) propyl phthalate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate Nonylphenoxy polyalkylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, and the like.

  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 hydroxyl group in one molecule. And a urethane compound obtained by a reaction between a group and a compound having a (meth) acryl group (such as 2-hydroxypropyl acrylate and oligopropylene glycol monomethacrylate). Specifically, there is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (manufactured by NOF Corporation, Blemma PP1000).

(B) The ratio with respect to the whole photosensitive resin composition of the 1 or more types of compound which consists of a group of the said general formula (III), (IV), (V) is the range of 3-70 mass%. From the viewpoint of resolution, it is 3% 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 3-30 mass% or less. Further, the ratio of the entire photopolymerizable unsaturated compound including the component (b) to the entire photosensitive resin composition is preferably 3% by mass or more from the viewpoint of sensitivity, and preferably 70% by mass or less from the viewpoint of edge fuse. More preferably, it is 10-60 mass%, More preferably, it is 15-55 mass%.
In the present invention, (c) a 2,4,5-triary imidazole dimer represented by the following general formula (VI) as a photopolymerization initiator is a preferred embodiment from the viewpoint of high resolution. is there.

（式中、Ｘ、Ｙ、及びＺはそれぞれ独立に水素、アルキル基、アルコキシ基及びハロゲン基のいずれかを表し、ｐ、ｑ、及びｒはそれぞれ独立に１〜５の整数である。）
上記一般式（ＶＩ）で表される化合物においては、２個のロフィン基を結合する共有結合は、１，１’−、１，２’−、１，４’−、２，２’−、２，４’−又は４，４’−位についているが、１，２’−位についている化合物が好ましい。２，４，５−トリアリ-ルイミダゾ−ル二量体には、例えば、２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾ−ル二量体、２−（ｏ−クロロフェニル）−４，５-ビス−（ｍ−メトキシフェ
ニル）イミダゾ−ル二量体、２−（ｐ−メトシキフェニル）−４，５-ジフェニルイミダゾ−ル二量体等があるが、特に、２−（ｏ−クロロフェニル）−４，５-ジフェニルイミ
ダゾ−ル二量体が好ましい。

(In the formula, X, Y, and Z each independently represent any of hydrogen, an alkyl group, an alkoxy group, and a halogen group, and p, q, and r are each independently an integer of 1-5.)
In the compound represented by the above general formula (VI), the covalent bond connecting 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 2,4,5-triary-imidazole 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., in particular, 2- (o-chlorophenyl) ) -4,5-diphenylimidazole dimer is preferred.

  As the photopolymerization initiator (c) used in the present invention, there is a system in which 2,4,5-triary-imidazole dimer represented by the above general formula (VI) and p-aminophenyl ketone are used in combination. preferable. Examples of p-aminophenyl ketone include p-aminobenzophenone, p-butylaminoacetophenone, p-dimethylaminoacetophenone, p-dimethylaminobenzophenone, p, p'-bis (ethylamino) benzophenone, p, p'- Bis (dimethylamino) benzophenone [Michler's ketone], p, p′-bis (diethylamino) benzophenone, p, p′-bis (dibutylamino) benzophenone, and the like.

  In addition to the compounds shown above, other photopolymerization initiators can be used in combination. Here, the photopolymerization initiator is a compound that is activated by various actinic rays such as ultraviolet rays to initiate polymerization. Examples of other photopolymerization initiators include quinones such as 2-ethylanthraquinone and 2-tert-butylanthraquinone, aromatic ketones such as benzophenone, benzoin, benzoin methyl ether, and benzoin ethyl ether. Examples include benzoin ethers, acridine compounds such as 9-phenylacridine, benzyldimethylketal, and benzyldiethylketal. 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. Further, N-aryl-α-amino acid compound, 1-phenyl-3- (4-tert-butyl-styryl) -5- (p-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzo Pyrazolines represented by oxazol-2-yl) phenyl) -3- (4-tert-butylstyryl) -5- (4-tert-butylphenyl) -pyrazoline can also be used. N-phenylglycine is particularly preferred.

In the photosensitive resin composition of the present invention, the ratio of the (c) photopolymerization initiator 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.
A basic dye can be used for the photosensitive resin composition in the present invention. Specific examples of basic dyes include fuchsin, phthalocyanine green, olamine base, chalcoxide green S, paramadienta, crystal violet, methyl orange, Nile Bull-2B, malachite green (Eizen (Hodogaya Chemical Co., Ltd.) (Registered trademark) MALACHITE GREEN), Basic Bull-20, Diamond Green (Hodogaya Chemical Co., Ltd., Eisen (registered trademark) DIAMOND GREEN GH), Victoria Bull-(Hodogaya Chemical Co., Ltd., Eisen (registered trademark) VICTORIA PURE BLUE) and the like.

  The photosensitive resin composition in the present invention may contain a coloring dye that develops color when irradiated with light. Examples of the coloring dye used 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. .

Halogen compounds 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, triazine compounds and the like. 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.
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 a radical polymerization inhibitor. Examples of such radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p- Examples include cresol, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), diphenylnitrosamine and the like. .

Furthermore, you may make the photosensitive resin composition of this invention contain additives, such as a plasticizer, as needed. Examples of such additives include phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, and tri-acetyl citrate. Examples thereof include n-propyl, tri-n-butyl acetylcitrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether.
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 substrate film that normally transmits actinic rays is used. Examples of such a substrate film include polyethylene, polypropylene, polycarbonate, polyethylene terephthalate having a thickness of about 10 μm to 100 μm. Although there is a synthetic resin film, a polyethylene terephthalate having appropriate flexibility and strength is usually 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 the present invention varies depending on the use, the upper limit of the thickness is preferably 100 μm or less, more preferably 50 μm or less, further preferably 30 μm or less, and most preferably 10 μm or less. The lower limit is preferably 0.5 μm or more, and more preferably 1 μm or more.

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.
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.
(3) Development process The process of forming a resist pattern on a substrate by peeling or removing the unexposed part of the photosensitive resin layer using an alkali developer after peeling off the support.

(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 A 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 and foreign matter as much as possible, exposure (proximity exposure) may be performed with the photomask floating above the support (A) by several tens to several hundreds of μm.
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 (B), but an aqueous sodium carbonate solution of 0.5% to 3% is generally used.

The (4) etching step is performed by a method suitable for the DFR used, such as acidic etching or alkaline etching.
As the alkaline stripping solution used in the above (5) stripping step, generally an alkaline aqueous solution that is stronger than the alkaline aqueous solution used in the development, for example, an aqueous solution of 1% or more and 5% or less of sodium hydroxide or potassium hydroxide. Can 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.
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 Sample The photosensitive resin laminates in Examples and Comparative Examples were produced as follows.
<Preparation of photosensitive resin laminate>
The photosensitive resin composition having the composition shown in Table 1 is thoroughly stirred and mixed, and uniformly coated on the surface of a 16 μm-thick polyethylene terephthalate film as a support using a bar coater, and dried in a dryer at 95 ° C. for 1 minute. Thus, a photosensitive resin layer was formed. The thickness of the photosensitive resin layer was 4 μm.
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>
As a substrate for evaluating resolution, adhesion, and etching characteristics, Esperflex made by Sumitomo Metals Co., Ltd., in which an 8 μm copper foil was laminated with an insulating resin, was used.
<Laminate>
While peeling off the polyethylene film of the photosensitive resin laminate, the photosensitive resin laminate was laminated to the substrate at a roll temperature of 105 ° C. with a hot roll laminator (AL-70, manufactured by Asahi Kasei Co., Ltd.). The air pressure was 0.35 MPa, and the laminating speed was 1.0 m / min.

<Exposure>
15 minutes after the above <laminate>, a glass chrome line mask film necessary for the evaluation of the photosensitive resin layer is placed on a polyethylene terephthalate film as a support on a substrate laminated with a photosensitive resin laminate. Then, it was exposed with an ultra high pressure mercury lamp (OMW Seisakusho, HMW-801) at an exposure amount of 100 mJ / cm ² . The line mask line / space is 1: 1.

<Development>
Subsequent to the above <exposure>, after peeling the polyethylene terephthalate film of the photosensitive resin laminate of the substrate on which the photosensitive resin laminate is laminated, a 0.5 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. is sprayed for a predetermined time. Then, the unexposed portion of the photosensitive resin layer was dissolved and removed. 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.
<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) Evaluation of Aggregability The photosensitive layer (resist layer) having a thickness of 40 μm and an area of 0.15 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 Spraying was performed using an apparatus at a spray pressure of 0.1 MPa for 3 hours. Thereafter, the developer was allowed to stand for 3 days, 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. A composition having good developer cohesiveness does not generate these aggregates at all, or even if they are generated, they can be easily washed away 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 aggregates are floating in the developer.
It is impossible to wash everything away with water, and most of it remains.

(2) Resolution Evaluation Following the above <Exposure>, in <Development>, spraying with a developer of a 0.5 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. was performed in a time twice as long as the minimum development time, The minimum mask line 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 5 μm or less ○: Resolution value of more than 5 μm and 10 μm or less Δ: Resolution value of more than 10 μm, 15 μm or less ×: Resolution value of more than 15 μm

(3) Adhesion evaluation Development was performed in the same manner as in (2) above, and the minimum mask width in which a cured resist line was normally formed was defined as an adhesion value, and the adhesion was ranked as follows.
◎: Adhesion value 5 μm or less ○: Adhesion value exceeds 5 μm, 10 μm or less Δ: Adhesion value exceeds 10 μm, 15 μm or less ×: Adhesion value exceeds 15 μm

(4) Resist shape Development was performed in the same manner as in (2) above. The shapes of 10 μm lines of the obtained cured patterns were ranked according to the following.
(Double-circle): The cut | disconnection of the foot part of a cured resist is favorable and there is no soot pull.
◯: The cut portion of the cured resist has a good cut and minimal pulling.
(Triangle | delta): The soot pull of 3 micrometers or less is recognized by the foot part of a cured resist.
X: Soo pulling exceeding 3 μm is observed in the foot portion of the cured resist.

(5) Etching characteristics Developed in the same manner as in (2) above, and then the resist was peeled off after etching for 3 times the minimum etching time at 3 ° C hydrochloric acid, 250 g / l cupric chloride at 50 ° C. Thus, a substrate on which a copper line was formed was obtained. The shape of the formed copper line was observed with an optical microscope and ranked according to the following rank.
○: The formed copper line is satisfactorily formed without any backlash.
Δ: Some rattling is observed on the formed copper line.
X: Roughness is observed in all formed copper lines.

3. Evaluation Results Table 1 shows the evaluation results of Examples and Comparative Examples. The mass parts of P-1 to P-2 in Table 1 are amounts containing methyl ethyl ketone. In Table 1, Comparative Example 1 lacks the compound represented by the above general formula (I) or (II).

<Symbol explanation>
P-1: Methyl ethyl ketone solution of a binary copolymer of 80% by weight of benzyl methacrylate and 20% by weight of methacrylic acid (solid content concentration 50% by weight, weight average molecular weight 25,000, acid equivalent 430, dispersity 2.7)
P-2: Methyl methacrylate 50% by weight, methacrylic acid 25% by weight, styrene 25% by weight
A methyl ethyl ketone solution of a terpolymer of (solid content concentration 35% by weight, weight average molecular weight 50,000, acid equivalent 344, dispersity 3.1)

M-1: Polyalkylene glycol dimethacrylate having an average of 3 moles added to both ends of polypropylene glycol with an average of 12 moles of propylene oxide added to both ends M-2: Bisphenol A at both ends Polyalkylene glycol dimethacrylate M-3 added with an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide, respectively. Polyethylene glycol with an average of 2 mol of ethylene oxide added to both ends of bisphenol A. Dimethacrylate (NK SEL BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.)

M-4: Dimethacrylate of polyethylene glycol with an average of 5 moles of ethylene oxide added to both ends of bisphenol A (NSK SL BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.)
M-5: 2,2-bis {4- (methacryloxypentaethoxy) cyclohexyl} propane M-6: hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (Nippon Yushi Co., Ltd., BLEMMA-PP1000 Polyurethane glycol dimethacrylate M-7: trimethylolpropane trimethacrylate M-8: trioxyethyltrimethylolpropane triacrylate (Shin Nakamura Chemical Co., Ltd.) NK ester A-TMPT-3EO)

G-1: 4,4′-bis (diethylamino) benzophenone G-2: 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer J-1: Diamond green (Hodogaya Chemical Co., Ltd.) Eisen (registered trademark)
DIAMOND GREEN GH)
J-2: Leuco Crystal Violet K-1: TINUVIN (registered trademark) manufactured by Ciba Specialty Chemicals Co., Ltd., wherein R ₁ , R ₂ , R ₃ , and R ₄ are normal butyl groups in the general formula (I) 460
K-2: CGL777MPA D manufactured by Ciba Specialty Chemicals Co., Ltd. _, wherein R _1, R ₃ , R ₄ are CH (CH ₃ ) COOC ₈ H ₁₇ and R ₂ is H in the general formula (I)
K-3: Ciba Specialty Chemicals wherein R ₅ is CH (CH ₃ ) COOC ₈ H ₁₇ (iso-octyl), R ₆ is H, R ₇ and R ₈ are phenyl groups in the general formula (II) ( TINUVIN (registered trademark) 479 manufactured by KK

L-1: 1: 1 mixture of 1- (2-di-n-butylaminomethyl) -5-carboxylbenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxylbenzotriazole L- 2: 3,5-di-t-butyl-4-hydroxyphenylpropionic acid tetraester of pentaerythritol (IRGANOX (registered trademark) 245 manufactured by Ciba Specialty Chemicals)

  According to the present invention, a printed wiring board, a flexible wiring board, a substrate for COF (chip on film), a lead frame, a substrate for semiconductor packaging, a transparent electrode for liquid crystal, a wiring for TFT for liquid crystal, a plasma display panel (PDP) In the field of manufacturing a conductor pattern such as an electrode for a display panel), it is suitable as an etching resist or a plating resist.

Claims (7)

(A) Carboxylic acid or acid anhydride having a carboxyl group content of 100 to 600 in terms of acid equivalent and a weight average molecular weight of 5,000 to 500,000 and having at least one polymerizable unsaturated group in the molecule And a binder resin obtained by copolymerizing one or more monomers each from a non-acidic monomer having a polymerizable unsaturated group in the molecule, (b) photopolymerization An unsaturated compound, (c) a photopolymerization initiator, and (d) one or more compounds selected from the following general formulas (I) and (II) : (b) a photopolymerizable unsaturated compound A photosensitive resin composition comprising at least one compound selected from the group of the following general formulas (III), (IV) and (V) as a compound .

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are H, an alkyl group having 1 to 10 carbon atoms, an aryl group or CH (CH ₃ ) COOC ₈ H ₁₇ , which may be the same or different. You may do it.)

(Wherein R ₅ , R ₆ , R ₇ and R ₈ are H, an alkyl group having 1 to 10 carbon atoms, an aryl group or CH (CH ₃ ) COOC ₈ H ₁₇ , which are the same or different. May be.)

(In the formula, Q ₁ and Q ₂ are H or CH ₃ , and these may be the same or different. A and B are an ethylene group or a propylene group, and each is the same. In the case where they are different, the repeating unit of-(A-O)-and-(B-O)-may be a block structure or a random structure: n ₁ , n ₂ , n ₃ , And n ₄ are each independently 0 or a positive integer, and the sum of these is 2 to 40.)

(In the formula, Q ₃ and Q ₄ are H or CH ₃ , and these may be the same or different. D and E are an ethylene group or a propylene group, and each is the same. In the case where they are different, the repeating unit of-(D-O)-and-(EO)-may be a block structure or a random structure, n ₅ , n ₆ , n ₇ , And n ₈ are each independently 0 or a positive integer, and the sum of these is 2 to 40.)

(In the formula, Q ₅ and Q ₆ are H or CH ₃ , which may be the same or different, and m ₁ , m ₂ and m ₃ are each independently an integer of 3 to 20. )   (A) Resin for binder: 20-90% by mass, (b) Photopolymerizable unsaturated compound: 3-70% by mass, (c) Photopolymerization initiator: 0.1-20% by mass, and (d) above The photosensitive resin composition according to claim 1, comprising 0.05 to 5% by mass of one or more compounds selected from the group of the general formulas (I) and (II).   The resin for binder (a) contains benzyl (meth) acrylate as a monomer of the non-acidic compound having one polymerizable unsaturated group in the molecule. Photosensitive resin composition. (C) As a photoinitiator, the compound represented by the following general formula (VI) is contained, The photosensitive resin composition of any one of Claims 1-3 characterized by the above-mentioned.

(In the formula, X, Y, and Z each independently represent any of hydrogen, an alkyl group, an alkoxy group, and a halogen group, and p, q, and r are each independently an integer of 1 to 5). It has the photosensitive resin composition of any one of Claims 1-4 on a support body, The photosensitive resin laminated body characterized by the above-mentioned. A method for forming a resist pattern, comprising: laminating the photosensitive resin laminate according to claim 5 on a surface of a metal plate or a metal-coated insulating plate, exposing and developing to remove an unexposed portion. A method for producing a conductor pattern, comprising etching or plating a substrate on which a resist pattern is formed by the method according to claim 6 .