JPWO2007125992A1 - Photosensitive resin laminate - Google Patents

Abstract

Photosensitive resin laminate that exhibits high resolution and high adhesion, has no backlash on the resist pattern side wall, has no dents on the resist pattern surface, and has extremely small skirts after development. The present invention provides a photosensitive resin laminate having no problem with the support film peelability. A photosensitive resin laminate obtained by sequentially laminating an intermediate layer having a layer thickness of 0.1 μm or more and 10 μm or less and a photosensitive resin layer on a support film, the intermediate layer comprising polyvinyl alcohol, a specific layer A photosensitive resin laminate comprising a compound is used.

Description

  The present invention relates to a photosensitive resin laminate and its use. More specifically, a printed wiring board having a conductor pattern, a flexible substrate, a lead frame substrate, a substrate for COF (Chip On Film), a substrate for a semiconductor package, and a transparent electrode for liquid crystal as a conductor pattern, for driving a liquid crystal The present invention relates to a photosensitive resin laminate suitable for manufacturing a substrate having TFT (Thin Film Transistor) wiring and PDP (Plasma Display Panel) electrodes, a method of forming a resist pattern using the same, and a method of manufacturing a conductor pattern.

  For electronic devices such as personal computers and mobile phones, for example, printed wiring boards are used as component and semiconductor mounting boards. Conventionally, as a resist used for manufacturing a printed wiring board, a photosensitive resin layer is formed by laminating a photosensitive resin layer on a support film and, if necessary, further laminating a protective layer on the photosensitive resin layer. A so-called dry film resist is used.

  As the photosensitive resin layer used here, an alkali developing type using a weak alkaline aqueous solution as a developing solution is generally used.

  A general method for producing a printed wiring board using a dry film resist will be briefly described. First, when there is a protective layer, the protective layer is peeled off. Thereafter, a photosensitive resin layer integrated with the support film is laminated on a permanent circuit forming substrate, for example, a copper clad laminate or a flexible substrate, using a laminator. Next, exposure is performed through a wiring pattern mask film. Exposure methods are diversified depending on the application. There is also a maskless exposure that does not require a photomask, for example, a direct drawing method using a laser. Next, if the supporting film remains, the resist film is peeled off, and the photosensitive resin layer in the unexposed part is dissolved or dispersed and removed by a developer, and then cured on the substrate (hereinafter referred to as a resist pattern). To form.

  After forming the resist pattern, the process for forming a circuit is roughly divided into two methods. The first method is a method (etching method) in which after removing the copper surface of the substrate not covered with the resist pattern by etching, the resist pattern portion is removed with an alkaline aqueous solution stronger than the developer. The second method is a method (plating method) of removing the resist pattern after etching the copper surface of the substrate using copper, solder, and nickel, and further etching the copper surface of the substrate that appears. is there. For the etching, cupric chloride, ferric chloride, and a copper ammonia complex solution are used.

  In recent years, in order to meet the demand for miniaturization of the conductor pattern of a printed wiring board, high resolution and adhesion of a resist pattern have been demanded (Patent Document 1). High resolution is generally achieved by improving the crosslink density of the photosensitive resin composition. However, if the crosslink density is increased, the resist pattern after exposure becomes hard and brittle. In the transport process up to the plating process, there may be a problem that a part of the resist pattern is missing. In particular, in the case of a thin film having a photosensitive resin layer thickness of 10 μm or less, light may be reflected from the substrate surface during exposure, and even the photosensitive resin layer that should be unexposed may be exposed. Since the exposed portion is reflected in the resist pattern, it may cause a short circuit. Further, when the light is reflected on the surface of the base material during exposure, a development residue called a soot may be generated on the bottom surface of the resist pattern. Depending on the size of the soot, there may be a problem in that the copper circuit is rattled during the etching process.

  A polyester film is generally used as a support film for the dry film resist. The polyester film contains a trace component such as a lubricant. This trace component causes a phenomenon that a very small part is shielded during exposure. As a result, rattling or dents may occur on the sidewall (side wall) of the resist pattern or on the surface (front surface) facing the substrate in the resist pattern. In particular, when a fine wiring having a conductor pattern width of 10 μm or less is formed, this influence cannot be ignored.

  As another means for achieving high resolution, a method of providing an intermediate layer made of polyvinyl alcohol between a support film and a photosensitive resin layer is known. By exfoliating the support film before the exposure step and exposing from the intermediate layer, it is possible to eliminate the influence on the resist pattern shape due to the high resolution and the trace components contained in the support film. However, when the intermediate layer is formed of polyvinyl alcohol alone, there may be a problem in the peelability from the support film and the solubility in an alkali developer.

  Patent Document 2 discloses a technique of providing an intermediate layer containing polyvinyl alcohol and hydroxyethyl cellulose. However, with this technique, it is extremely difficult to control the peelability of the film between the support film and the intermediate layer, and it is necessary to devise the intermediate layer composition.

  Patent Document 3 discloses a technique in which an oxypropylene group-containing polyvinyl alcohol resin is used for the intermediate layer, and a (meth) acrylic acid partial ester of a polyhydric alcohol is used for the photosensitive resin layer. In Patent Document 4, the intermediate layer is at least selected from the group consisting of polyvinyl alcohol obtained by copolymerizing a specific amount of olefin, polyethylene oxide having a polymerization degree of 4000 or more, carboxyl group-containing acrylate resin, and a copolymer of dibasic acid and olefin. Although a technique having one type as a main component is disclosed, these methods are still unsolved with respect to problems of high resolution, high adhesion, and resist pattern swindle after development.

  For the production of printed wiring boards with fine conductor patterns, the production of COF substrates that require high resolution with thin films, and the production of substrates for semiconductor packages, the resist pattern shape after development exhibits high resolution. Therefore, there has been a demand for a photosensitive resin composition and a photosensitive resin laminate having characteristics that the side wall has no backlash, the surface thereof is not dented, and the width after development is extremely small. .

JP 2001-159817 A JP-A 63-197942 JP-A-4-371957 JP-A-6-242611

  The present invention is a photosensitivity that exhibits high resolution and high adhesion, has no backlash on the side wall of the resist pattern, has no dents on the surface of the resist pattern, and has extremely small soot after development. Providing a photosensitive resin laminate that is a support resin peelable and has no problem with support film peelability, and a method for forming a resist pattern using the laminate and a method for producing a conductor pattern With the goal.

  As a result of studying the present inventors to solve the above-mentioned problems, there is no problem in the peelability of the support film by using a specific photosensitive resin laminate, and high resolution and high adhesion are developed after development. In addition, the inventors have found that it is possible to provide a photosensitive resin laminate in which there is no backlash on the side wall of the resist pattern, there is no dent on the surface of the resist pattern, and the width after development is extremely small. It was.

That is, this invention is invention of the following photosensitive resin laminated bodies, the resist pattern formation method, and the manufacturing method of a conductor pattern.
(1) A photosensitive resin laminate comprising a support film, and an intermediate layer and a photosensitive resin layer having a layer thickness of 0.1 μm or more and 10 μm or less on the support film in this order, the intermediate layer comprising: The said photosensitive resin laminated body characterized by containing polyvinyl alcohol and 1 or more types of compounds chosen from the group which consists of a compound represented with the following general formula (I).
_{R 1 -O- (CH 2 CH 2} O) n 1 -R 2 (I)
(R ₁ and R ₂ are H or CH ₃ , which may be the same or different, and n ₁ is an integer from 3 to 25.)
(2) The photosensitive resin laminate according to (1), wherein a protective layer is further laminated on the photosensitive resin layer.

(3) The said photosensitive resin layer is (a) Resin for binders whose carboxyl group content is 100-600 in an acid equivalent, and whose weight average molecular weight is 5000-500000: 20-90 mass%, (b) At least (1) or a layer composed of a photosensitive resin composition containing one type of photopolymerizable unsaturated compound: 3-70% by mass, and (c) a photopolymerization initiator: 0.1-20% by mass. The photosensitive resin laminate according to (2).
(4) The photosensitive resin laminate according to (3), wherein the resin for binder (a) contains benzyl (meth) acrylate as a copolymerization component.

（式中、Ｒ_４及びＲ_５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、ｎ_３、ｎ_４及びｎ_５は、それぞれ独立に３〜２０の整数である。）

（式中、Ｒ_６及びＲ_７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、ＡはＣ_２Ｈ_４、ＢはＣＨ_２ＣＨ（ＣＨ_３）、ｎ_６＋ｎ_７は２〜４０の整数、ｎ_８＋ｎ_９は０〜４０の整数、ｎ_６及びｎ_７は、それぞれ独立に１〜３９の整数、ｎ_８及びｎ_９は、それぞれ独立に０〜４０の整数である。−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよい。ブロックの場合、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の順序は、何れがビスフェニル基側であってもよい。）

（式中、Ｒ_８及びＲ_９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、ＤはＣ_２Ｈ_４、ＥはＣＨ_２ＣＨ（ＣＨ_３）、ｍ_１＋ｍ_２は２〜４０の整数、ｍ_３＋ｍ_４は０〜４０の整数、ｍ_１及びｍ_２は、それぞれ独立に１〜３９の整数、ｍ_３及びｍ_４は、それぞれ独立に０〜４０の整数である。−（Ｄ−Ｏ）−及び−（Ｅ−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよい。ブロックの場合、−（Ｄ−Ｏ）−及び−（Ｅ−Ｏ）−の順序は、何れがシクロヘキシル基側であってもよい。）

（式中、Ｒ_１０は、炭素数４〜１２の2価の有機基、Ｒ_１１及びＲ_１２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い。ｍ_５及びｍ_６は、それぞれ独立に１〜１５の整数である。）

（式中、Ｒ_１３は、Ｈ又はＣＨ_３、Ｒ_１４は炭素数４〜１４のアルキル基、Ａ’はＣ_２Ｈ_４、Ｂ’はＣＨ_２ＣＨ（ＣＨ_３）、ｍ_７は１〜１２、ｍ_８は０〜１２、ｍ_９は０〜３の整数である。−（Ａ’−Ｏ）−及び−（Ｂ’−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよい。ブロックの場合、−（Ａ’−Ｏ）−及び−（Ｂ’−Ｏ）−の順序は、何れがフェニル基側であってもよい。）(5) (b) at least one photopolymerizable unsaturated compound selected from the group consisting of compounds represented by the following general formulas (II) to (VI): The photosensitive resin laminate according to (3) or (4), which is a compound.

(In the formula, R ₄ and R ₅ are H or CH ₃ , which may be the same or different, and n ₃ , n ₄ and n ₅ are each independently an integer of 3 to 20) is there.)

Wherein R ₆ and R ₇ are H or CH ₃ , which may be the same or different, A is C ₂ H ₄ , B is CH ₂ CH (CH ₃ ), n ₆ + N ₇ is an integer of 2 to 40, n ₈ + n ₉ is an integer of 0 to 40, n ₆ and n ₇ are each independently an integer of 1 to 39, and n ₈ and n ₉ are each independently 0 to 40 The arrangement of repeating units of-(AO)-and-(B-O)-may be random or block, and in the case of a block,-(AO)-and Any order of-(B-O)-may be on the bisphenyl group side.)

(Wherein R ₈ and R ₉ are H or CH ₃ , which may be the same or different, D is C ₂ H ₄ , E is CH ₂ CH (CH ₃ ), m ₁ + M ₂ is an integer of ₂ to 40, m ₃ + m ₄ is an integer of 0 to 40, m ₁ and m ₂ are each independently an integer of ₁ to 39, and m ₃ and m ₄ are each independently 0 to 40 The arrangement of repeating units of-(DO)-and-(EO)-may be random or block, and in the case of a block,-(DO)-and Any of the order of-(E-O)-may be on the cyclohexyl group side.)

(Wherein R ₁₀ is a divalent organic group having 4 to 12 carbon atoms, R ₁₁ and R ₁₂ are H or CH ₃ , and these may be the same or different. M ₅ and m ₆ is each independently an integer of 1 to 15.)

(In the formula, R ₁₃ is H or CH ₃ , R ₁₄ is an alkyl group having 4 to ₁₄ carbon atoms, A ′ is C ₂ H ₄ , B ′ is CH ₂ CH (CH ₃ ), and m ₇ is 1 to 12. , M ₈ is an integer from 0 to 12, and m ₉ is an integer from 0 to 3. The sequence of repeating units of-(A'-O)-and-(B'-O)-is a block even if it is random. In the case of a block, any of the order of-(A'-O)-and-(B'-O)-may be on the phenyl group side.)

(6) Laminating step of laminating the photosensitive resin laminate according to any one of (1) to (5) on the surface of a metal plate or a metal-coated insulating plate, an exposure step of peeling the support film and exposing A method for forming a resist pattern comprising sequentially developing steps of removing unexposed portions by development.
(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, there is no problem in the peelability of the support film, and after development, high resolution and high adhesion are developed, the resist pattern sidewalls are free of backlash, the resist pattern surface is free of dents, and development is performed. It is possible to provide a photosensitive resin laminate having a very small skirt and a method for forming a resist pattern and a method for producing a conductor pattern using the laminate.

FIG. 1 is a schematic view of a photosensitive resin laminate according to the present invention (the above item (1)). FIG. 2 is a schematic view of the photosensitive resin laminate of the present invention (item (2) above).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Support film 2 Intermediate | middle layer 3 Photosensitive resin layer 4 Protective layer

Hereinafter, the present invention will be specifically described.
The photosensitive resin laminate of the present invention is a photosensitive resin laminate in which an intermediate layer having a layer thickness of 0.1 μm or more and 10 μm or less and a photosensitive resin layer are sequentially laminated on a support film.

The photosensitive resin laminate of the present invention is characterized in that the intermediate layer contains polyvinyl alcohol and one or more compounds selected from the group consisting of compounds represented by the following general formula (I). And
_{R 1 -O- (CH 2 CH 2} O) n 1 -R 2 (I)
(R ₁ and R ₂ are H or CH ₃ , which may be the same or different, and n ₁ is an integer from 3 to 25.)

  The blending weight ratio of the polyvinyl alcohol in the intermediate layer is preferably 50% by mass or more and 95% by mass or less from the viewpoint of developability and cost. More preferably, it is 70 mass% or more, More preferably, it is 75 mass% or more and 90 mass% or less.

  The blending weight ratio of the compound of the general formula (I) in the intermediate layer is preferably 5% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 30% by mass from the viewpoint of peelability between the support film and the intermediate layer. Or less, more preferably 5% by mass or more and 15% by mass or less.

  Polyvinyl alcohol is generally produced by saponifying polyvinyl acetate. The weight average molecular weight of the polyvinyl alcohol used in the present invention is preferably 1,000 to 100,000. A more preferred weight average molecular weight is 5,000 to 50,000 from the viewpoint of oxygen barrier properties and developability. Further, the saponification degree is preferably 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more from the viewpoint of developability.

  The weight average molecular weight of the polyvinyl alcohol used in the photosensitive resin laminate of the present invention is gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Showa Denko K.K.). It is calculated | required as a weight average molecular weight (polystyrene conversion) by manufactured Shodex (trademark) (HFIP-805, HFIP-803) 2 series, moving bed solvent: Hexafluoroisopropanol and the calibration curve use with a polystyrene standard sample.

In the compound represented by the general formula (I), n ₁ is preferably 3 or more from the viewpoint of odor, and n ₁ is preferably 25 or less from the viewpoint of compatibility with polyvinyl alcohol and developability. n ₁ is more preferably 5 or more and 20 or less, and still more preferably 7 or more and 15 or less. Specific examples of the compound represented by the general formula (I) include polyethylene glycol having an average molecular weight of 200 (PEG 200 manufactured by NOF Corporation), polyethylene glycol having an average molecular weight of 300 (PEG 300 manufactured by NOF Corporation, average) Polyethylene glycol having a molecular weight of 400 (PEG 400 manufactured by NOF Corporation), polyethylene glycol having an average molecular weight of 600 (PEG 600 manufactured by NOF Corporation), polyethylene glycol having an average molecular weight of 1000 (PEG 1000 manufactured by NOF Corporation), Polyethylene glycol monomethyl ether having an average molecular weight of 400 (Uniox M-400 manufactured by NOF Corporation), polyethylene glycol monomethyl ether having an average molecular weight of 550 (UNIOX M manufactured by NOF Corporation) 550), polyethylene glycol monomethyl ether is the average molecular weight of 1000 (manufactured by NOF Corporation Uniox M-1000).

  In addition to the above, a known water-soluble polymer may be added to the intermediate layer. Specific examples of the water-soluble polymer include polyvinyl ether-maleic anhydride water-soluble salts, carboxyalkyl starch water-soluble salts, polyacrylamide, polyamide, polyacrylic acid water-soluble salts, gelatin, polypropylene glycol, and polyvinylpyrrolidone. Specific examples of polyvinylpyrrolidone include K-15 having a weight average molecular weight of 40,000 manufactured by Nippon Shokubai Co., Ltd., K-30 having a weight average molecular weight of 100,000, K-85 having a weight average molecular weight of 900,000, There is K-90 with a weight average molecular weight of 1,000,000.

  The thickness of the intermediate layer is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 3 μm or less from the viewpoints of resolution, adhesion, and developability. Further, from the viewpoint of oxygen barrier properties, it is 0.1 μm or more, preferably 0.5 μm or more, more preferably 1 μm or more.

  In the present invention, it is preferable to peel off the support film before exposure in order to achieve high resolution. In the case where the support film is peeled before exposure, the support film may be transparent or opaque so as to transmit exposure light. Examples of the support film in the present invention include synthetic resin films represented by polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate having a thickness of 10 μm to 100 μm. Usually, polyethylene terephthalate having appropriate flexibility and strength is preferably used. In order to make it difficult to generate wrinkles during lamination and to prevent damage to the support film, the film thickness is preferably 10 μm or more.

  The photosensitive resin laminate of the present invention is excellent in the peelability of the support film when the intermediate layer adopts the above-described configuration. That is, when peeling a support film before an exposure process, it is the photosensitive resin laminated body whose interlayer adhesive force of a support film and an intermediate | middle layer is lower than an intermediate | middle layer and a photosensitive resin layer.

  Moreover, as a photosensitive resin laminated body of this invention, you may laminate | stack a protective layer further on the support film, after laminating | stacking an intermediate | middle layer and the photosensitive resin layer one by one.

  As a characteristic of the protective layer, it is important that the interlayer adhesive force between the photosensitive resin layer and the protective layer is lower than the interlayer adhesive force between the support film and the intermediate layer. Can be easily peeled off.

  As the protective layer, there are synthetic resin films represented by polyethylene, polypropylene, polycarbonate and polyethylene terephthalate having a thickness of 10 to 100 μm. Among these, a polyethylene film or a polypropylene film is preferably used.

  The upper limit of the film thickness of the photosensitive resin layer of the present invention 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 of the film thickness is preferably 0.5 μm or more, more preferably 1 μm or more.

  The photosensitive resin layer in the photosensitive resin laminate of the present invention has (a) a binder resin 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: 20 to 90% by mass. (B) at least one photopolymerizable unsaturated compound: 3 to 70% by mass, (c) a photopolymerization initiator: 0.1 to 20% by mass, and a layer made of a photosensitive resin composition. Is preferred.

The photosensitive resin composition used for the photosensitive resin laminate of the present invention will be described in detail below.
(A) As for the quantity of the carboxyl group contained in resin for binders, 100-600 are preferable by an acid equivalent, More preferably, it is 250-450, More preferably, it is 300-450. An acid equivalent means the mass of resin for binders which has 1 equivalent of carboxyl groups 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.

(A) It is preferable that the weight average molecular weight of resin for binders is 5,000-500,000. The weight average molecular weight of the binder resin is preferably 500,000 or less from the viewpoint of resolution, and is preferably 5000 or more from the viewpoint of edge fuse. In order to exhibit the effects of the present invention better, 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 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, weight average molecular weight and number average molecular weight (polystyrene) using polystyrene standard sample (use of calibration curve with Shodex STANDARD SM-105 manufactured by Showa Denko KK) Conversion) is required.

  (A) The binder resin 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, and maleic acid half ester. Among these, (meth) acrylic acid is particularly preferable. Here, (meth) acryl indicates acryl and methacryl. The same applies hereinafter.

  The second monomer is a non-acidic compound having one polymerizable unsaturated group in the molecule. The compound is selected so as to maintain the developability of the photosensitive resin layer, the resistance in the etching and plating processes, and the 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, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) ) Acrylate, phenyl (meth) acrylate, cresyl (meth) acrylate, naphthyl (meth) acrylate, vinyl compounds having a phenyl group (for example, styrene) can be used. That. In particular, benzyl (meth) acrylate is preferable from the viewpoint of resolution and developer aggregation.

  (A) The binder resin is a radical polymerization initiator, for example, 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 synthesize by adding appropriate amounts of benzoyl peroxide and azoisobutyronitrile and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

  (A) The ratio with respect to the whole photosensitive resin composition of resin for binders has the preferable range of 20-90 mass%, More preferably, it is 30-70 mass%. From the viewpoint that the resist pattern has sufficient resistance as a resist, for example, tenting, etching, and various plating processes, the resist pattern is preferably 20% by mass or more and 90% by mass or less.

（式中、Ｒ_４及びＲ_５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、ｎ_３、ｎ_４及びｎ_５は、それぞれ独立に３〜２０の整数である。）(B) The at least one photopolymerizable unsaturated compound is at least one light selected from the group consisting of compounds represented by the following general formulas (II) to (VI) from the viewpoint of high resolution. It is a preferable embodiment to use a polymerizable unsaturated compound in the photosensitive resin composition.

(In the formula, R ₄ and R ₅ are H or CH ₃ , which may be the same or different, and n ₃ , n ₄ and n ₅ are each independently an integer of 3 to 20) is there.)

（式中、Ｒ_６及びＲ_７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、ＡはＣ_２Ｈ_４、ＢはＣＨ_２ＣＨ（ＣＨ_３）、ｎ_６＋ｎ_７は２〜４０の整数、ｎ_８＋ｎ_９は０〜４０の整数、ｎ_６及びｎ_７は、それぞれ独立に１〜３９の整数、ｎ_８及びｎ_９は、それぞれ独立に０〜４０の整数である。−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよい。ブロックの場合、−（Ａ−Ｏ）−及び−（Ｂ−Ｏ）−の順序は、何れがビスフェニル基側であってもよい。）

Wherein R ₆ and R ₇ are H or CH ₃ , which may be the same or different, A is C ₂ H ₄ , B is CH ₂ CH (CH ₃ ), n ₆ + N ₇ is an integer of 2 to 40, n ₈ + n ₉ is an integer of 0 to 40, n ₆ and n ₇ are each independently an integer of 1 to 39, and n ₈ and n ₉ are each independently 0 to 40 The arrangement of repeating units of-(AO)-and-(B-O)-may be random or block, and in the case of a block,-(AO)-and Any order of-(B-O)-may be on the bisphenyl group side.)

（式中、Ｒ_８及びＲ_９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、ＤはＣ_２Ｈ_４、ＥはＣＨ_２ＣＨ（ＣＨ_３）、ｍ_１＋ｍ_２は２〜４０の整数、ｍ_３＋ｍ_４は０〜４０の整数、ｍ_１及びｍ_２は、それぞれ独立に１〜３９の整数、ｍ_３及びｍ_４は、それぞれ独立に０〜４０の整数である。−（Ｄ−Ｏ）−及び−（Ｅ−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよい。ブロックの場合、−（Ｄ−Ｏ）−及び−（Ｅ−Ｏ）−の順序は、何れがシクロヘキシル基側であってもよい。）

(Wherein R ₈ and R ₉ are H or CH ₃ , which may be the same or different, D is C ₂ H ₄ , E is CH ₂ CH (CH ₃ ), m ₁ + M ₂ is an integer of ₂ to 40, m ₃ + m ₄ is an integer of 0 to 40, m ₁ and m ₂ are each independently an integer of ₁ to 39, and m ₃ and m ₄ are each independently 0 to 40 The arrangement of repeating units of-(DO)-and-(EO)-may be random or block, and in the case of a block,-(DO)-and Any of the order of-(E-O)-may be on the cyclohexyl group side.)

（式中、Ｒ_１０は、炭素数４〜１２の２価の有機基、Ｒ_１１及びＲ_１２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い。ｍ_５及びｍ_６は、それぞれ独立に１〜１５の整数である。）

(Wherein R ₁₀ is a divalent organic group having 4 to 12 carbon atoms, R ₁₁ and R ₁₂ are H or CH ₃ , and these may be the same or different. M ₅ and m ₆ is each independently an integer of 1 to 15.)

（式中、Ｒ_１３は、Ｈ又はＣＨ_３、Ｒ_１４は炭素数４〜１４のアルキル基、Ａ’はＣ_２Ｈ_４、Ｂ’はＣＨ_２ＣＨ（ＣＨ_３）、ｍ_７は１〜１２、ｍ_８は０〜１２、ｍ_９は０〜３の整数である。−（Ａ’−Ｏ）−及び−（Ｂ’−Ｏ）−の繰り返し単位の配列は、ランダムであってもブロックであってもよい。ブロックの場合、−（Ａ’−Ｏ）−及び−（Ｂ’−Ｏ）−の順序は、何れがフェニル基側であってもよい。）

(In the formula, R ₁₃ is H or CH ₃ , R ₁₄ is an alkyl group having 4 to ₁₄ carbon atoms, A ′ is C ₂ H ₄ , B ′ is CH ₂ CH (CH ₃ ), and m ₇ is 1 to 12. , M ₈ is an integer from 0 to 12, and m ₉ is an integer from 0 to 3. The sequence of repeating units of-(A'-O)-and-(B'-O)-is a block even if it is random. In the case of a block, any of the order of-(A'-O)-and-(B'-O)-may be on the phenyl group side.)

In the compound represented by the general formula (II), n ₃ , n ₄ and n ₅ are preferably 3 or more from the viewpoints of boiling point and odor. From the viewpoint of sensitivity due to the concentration of the photoactive site per unit mass, n ₃ , n ₄ and n ₅ are preferably 20 or less. Specific examples of the compound represented by the general formula (II) used in the present invention include, for example, a diglycol of glycol in which ethylene oxide is further added to both ends at an average of 3 moles on polypropylene glycol having an average of 12 moles of propylene oxide. Methacrylate is preferred.

In the compound represented by the general formula (III), n ₆ + n ₇ and n ₈ + n ₉ need to be 40 or less, and exceeding 40 is not preferable from the viewpoint of sensitivity. Preferably it is 30 or less.

  Specific examples of the compound represented by the general formula (III) used in the present invention include polyalkylene glycol dimethacrylate in which an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide are added to both ends of bisphenol A, respectively. Polyalkylene glycol dimethacrylate with an average of 2 moles of propylene oxide and an average of 15 moles of ethylene oxide at each end of bisphenol A Polyethylene glycol dimethacrylate with an average of 5 moles of ethylene oxide at each end of bisphenol A (Shin Nakamura) NK ester BPE-500 manufactured by Chemical Industry Co., Ltd.) and polyethylene glycol dimethacrylate (Shin Nakamura Chemical Co., Ltd.) with an average of 2 moles of ethylene oxide added to both ends of bisphenol A. There are K ester BPE-200).

In the compound represented by the general formula (IV), m ₁ + m ₂ and m ₃ + m ₄ need to be 40 or less, and exceeding 40 is not preferable from the viewpoint of sensitivity. Preferably it is 30 or less.

  Specific examples of the compound represented by the general formula (IV) include 2,2-bis {(4-acryloxypolyethyleneoxy) cyclohexyl} propane or 2,2-bis {(4-methacryloxypolyethyleneoxy) cyclohexyl}. Propane is mentioned. The polyethyleneoxy group of the compound is monoethyleneoxy group, diethyleneoxy group, triethyleneoxy group, tetraethyleneoxy group, pentaethyleneoxy group, hexaethyleneoxy group, heptaethyleneoxy group, octaethyleneoxy group, nonaethylene It is any group selected from the group consisting of an oxy group, a decaethyleneoxy group, an undecaethyleneoxy group, a dodecaethyleneoxy group, a tridecaethyleneoxy group, a tetradecaethyleneoxy group, and a pentadecaethyleneoxy group Compounds are preferred. Further, 2,2-bis {(4-acryloxypolyoxy) cyclohexyl} propane or 2,2-bis {(4-methacryloxypolyalkyleneoxy) cyclohexyl} propane may also be mentioned. Examples of the polyalkyleneoxy group possessed by the compound include a mixture of an ethyleneoxy group and a propyleneoxy group, an adduct having a block structure or a random structure having an octaethyleneoxy group and a dipropyleneoxy group, and tetraethyleneoxy. A block structure adduct or a random structure adduct of a group and a tetrapropyleneoxy group, a block structure adduct of a pentadecaethyleneoxy group and a dipropyleneoxy group, or an adduct of a random structure is preferable. Among these, 2,2-bis {(4-methacryloxypentaethyleneoxy) cyclohexyl} propane is most preferable.

In the compound represented by the general formula (V), when m ₅ or m ₆ exceeds 15, sufficient sensitivity cannot be obtained. In the formula, R10 is a divalent organic group having 4 to 12 carbon atoms and is a residue of diisocyanate.

  Specific examples of the compound represented by the general formula (V) include a diisocyanate compound such as hexamethylene diisocyanate, tolylene diisocyanate, or 2,2,4-trimethylhexamethylene diisocyanate, and a hydroxyl group in one molecule. A compound having a (meth) acrylic group, for example, a urethane compound with 2-hydroxypropyl acrylate and oligopropylene glycol monomethacrylate. Specifically, there is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (Nippon Yushi Co., Ltd., Bremma-PP1000).

In the compound represented by the general formula (VI), when m ₇ or m ₈ exceeds 12, sufficient sensitivity cannot be obtained. m ₉ is not sufficient sensitivity can be obtained even exceed 3.

  Specific examples of the compound represented by the general formula (VI) include, for example, an acrylate of a compound in which polypropylene glycol added with an average of 2 mol of propylene oxide and polyethylene glycol added with an average of 7 mol of ethylene oxide are added to nonylphenol. There is a certain 4-normal nonylphenoxyheptaethylene glycol dipropylene glycol acrylate. Examples also include 4-normalnonylphenoxyoctaethylene glycol acrylate (manufactured by Toagosei Co., Ltd., M-114), which is an acrylate of a compound obtained by adding polyethylene glycol added with an average of 8 moles of ethylene oxide to nonylphenol.

  (B) As a compound not belonging to the group consisting of compounds represented by the above general formulas (III), (IV), (V), (VI) and (VII) of at least one photopolymerizable unsaturated compound Are the photopolymerizable unsaturated compounds shown below. 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, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol tetra (meth) Acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycol Jirueteruji (meth) acrylate, beta-hydroxypropyl-beta '- (Akuriroirukishi) propyl phthalate, phenoxy polyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate.

  The ratio of the at least one photopolymerizable unsaturated compound selected from the group consisting of the compounds represented by the general formulas (II) to (VI) to the entire photosensitive resin composition is in the range of 3 to 70% by mass. It is. 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.

  (B) The ratio of the entire photopolymerizable unsaturated compound 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%.

（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。）(C) The photopolymerization initiator may be any compound that is activated by various actinic rays, for example, ultraviolet rays, and (b) initiates polymerization of a photopolymerizable unsaturated compound, and is represented by the following general formula (VII): The use of the 2,4,5-triarylimidazole dimer represented is a preferred embodiment from the viewpoint of high resolution.

(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 triarylimidazole dimer represented by the above general formula (VII), the covalent bond connecting two lophine groups is 1,1′-, 1,2′-, 1,4′-. 2,2′-, 2,4′- or 4,4′-bond, etc., but the compound of the above general formula (VII) in which the covalent bond is a 1,1′-bond is preferable. 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 and 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, especially 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer. A monomer is preferred.

  As the (c) photopolymerization initiator used in the present invention, a system in which the 2,4,5-triarylimidazole dimer represented by the general formula (VII) and p-aminophenyl ketone are used in combination is 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, and p, p′-bis (dibutylamino) benzophenone.

  Moreover, as photoinitiators other than the compound shown above, quinones, for example, 2-ethylanthraquinone, 2-tert-butylanthraquinone. Benzoin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, acridine compounds such as 9-phenylacridine, benzyl dimethyl ketal, and benzyl diethyl ketal. There are also combinations of thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and tertiary amine compounds such as dimethylaminobenzoic acid alkyl ester compounds. There are also oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzoyloxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime. Further, N-aryl-α-amino acid compounds can also be used, and among these, N-phenylglycine is particularly preferable.

  It is preferable that the photosensitive resin composition in the photosensitive resin laminate of the present invention contains (c) a photopolymerization initiator in an amount of 0.1 to 20% by mass with respect to the entire photosensitive resin composition. From the viewpoint of obtaining sufficient sensitivity, it is preferably 0.1% by mass or more and 20% by mass or less from the viewpoint of preventing light from being reflected from the substrate surface during exposure.

  A basic dye can be used for the photosensitive resin composition. Specific examples of basic dyes include fuchsin, phthalocyanine green, auramin base, chalcoxide green S, crystal violet, methyl orange, nile blue 2B, malachite green (Eisen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), Basic Blue 20 and Diamond Green (Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.) and Victoria Blue (Eisen (registered trademark) VICTORIA PURE BLUE manufactured by Hodogaya Chemical Co., Ltd.) are listed.

  The photosensitive resin composition 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 and a halogen compound. Examples of the leuco dye include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet] and tris (4-dimethylamino-2-methylphenyl) methane [leucomalachite green].

  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, halogenated triazine compounds. Examples of the halogenated triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine and 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine.

  Among such color developing dyes, a combination of tribromomethylphenyl sulfone and a leuco dye or a combination of a halogenated triazine compound and a leuco dye is useful.

  As for content of the halogen compound in the photosensitive resin composition in the case of containing a halogen compound, 0.01-5 mass% is preferable.

  The content in the case of containing the basic dye and the leuco dye 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.

  Furthermore, in order to improve the thermal stability and storage stability of the photosensitive resin composition of the present invention, it is preferable that the photosensitive resin composition contains a radical polymerization inhibitor and benzotriazoles.

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

  Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzo. Examples include triazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole. Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl). Examples include aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole.

  The total amount of each of the radical polymerization inhibitor and the benzotriazoles is preferably 0.01 to 3% by mass, and more preferably 0.05 to 1% by mass. This amount is preferably 0.01% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and more preferably 3% by mass or less from the viewpoint of maintaining photosensitivity.

  These radical polymerization inhibitors and benzotriazole compounds may be used alone or in combination of two or more.

  Furthermore, you may make the photosensitive resin composition contain a plasticizer as needed. 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 include n-propyl, tri-n-butyl acetylcitrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether. As content in the case of containing a plasticizer, 5-50 mass% is preferable in a 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.

  Hereinafter, with reference to FIG. 1 and FIG. 2, a method for producing a photosensitive resin laminate by sequentially laminating the support film 1, the intermediate layer 2, the photosensitive resin layer 3, and the protective layer 4 as necessary will be described.

  First, polyvinyl alcohol, for example, PVA-205 resin made by Kuraray Co., Ltd., and one or more compounds selected from the group consisting of compounds represented by the above general formula (I), the solid content ratio is 5 to 30 wt. %, Gradually added to water heated to 60 to 90 ° C., and stirred for about 1 hour to dissolve uniformly to obtain a uniform aqueous solution of the composition of the intermediate layer. The viscosity of the uniform aqueous solution of the intermediate layer composition containing polyvinyl alcohol is preferably adjusted to 10 to 500 mPa · s. Next, the aqueous solution is applied onto the support film 1 using a bar coater or a roll coater and dried to obtain the support film 1 with the intermediate layer 2.

  Separately, a preparation liquid of the photosensitive resin composition is prepared. It is preferable to add a solvent so that the viscosity of the preparation liquid of the photosensitive resin composition is 500 to 4000 mPa · sec at 25 ° C. Examples of the solvent used include ketones and alcohols typified by methyl ethyl ketone (MEK), such as methanol, ethanol, and isopropyl alcohol.

  The photosensitive resin layer 3 made of a photosensitive resin composition is applied on the intermediate layer of the support film 1 with the intermediate layer 2 by using a bar coater or a roll coater in the same manner as the application of the intermediate layer 2 and dried.

  Next, the photosensitive resin laminate can be produced by laminating the protective layer 4 on the photosensitive resin layer 3.

  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 which sticks using a hot roll laminator on a board | substrate, for example, a copper clad laminated board, or a flexible substrate, peeling off a protective layer, when a photosensitive resin laminated body has a protective layer.

(2) Exposure process The process of peeling a support film from the photosensitive resin laminated body, sticking the mask film which has a desired wiring pattern on an intermediate | middle layer, and exposing using an actinic-light source.

(3) Development step A step of dissolving or dispersing and removing the unexposed portions of the intermediate layer and the photosensitive resin layer using an alkali developer to form a cured resist pattern on the substrate.

(4) Etching process or plating process An etching solution is sprayed on the formed resist pattern to etch the copper surface not covered with the resist pattern, or copper, solder, nickel on the copper surface not covered with the resist pattern And a step of performing plating treatment represented by tin. Thereby, a conductor pattern can be manufactured.

(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 or foreign matter as much as possible, exposure (proximity exposure) may be performed in a state where the photomask is floated several tens of μm to several hundreds of μm from the support film.

  Examples of the alkaline developer used in the (3) development step include sodium carbonate or an aqueous solution of potassium carbonate. 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 or more and 3% by mass or less is used.

  The (4) etching step is performed by, for example, acid etching or alkali etching. A method suitable for the dry film resist to be used is selected.

  As the alkali stripping solution used in the above (5) stripping step, generally an alkaline aqueous solution stronger than the alkaline aqueous solution used in the development, for example, 1% by mass to 5% by mass of sodium hydroxide or potassium hydroxide An aqueous solution of

When a plating process is selected, the copper surface that appears under the resist pattern may be further 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.
[Examples 1-12] and [Comparative Examples 1-3]
1. Production of Evaluation Sample The photosensitive resin laminates in Examples and Comparative Examples were produced as follows.

<Preparation of photosensitive resin laminate>
First, the intermediate layer composition shown in Table 1-1 and Table 1-2 is gradually added to water heated to 85 ° C. so that the solid content ratio is 10% by mass, and stirred uniformly for about 1 hour. By dissolving, a uniform aqueous solution of the composition of the intermediate layer was obtained. A 16 μm-thick polyethylene terephthalate film was used as the support film, and the aqueous solution was applied onto the support film using a bar coater. Subsequently, it was dried in a dryer at 100 ° C. for 3 minutes to form a uniform intermediate layer on the support film. The thickness of the intermediate layer was 2 μm. On the intermediate layer laminated on the support film, the photosensitive resin composition shown in Table 1-1 and Table 1-2 is uniformly applied using a bar coater, and dried in a dryer at 95 ° C. for 3 minutes. A uniform photosensitive resin layer was formed. The thickness of the photosensitive resin layer was 3 μm.

  Next, a 25 μm thick polyethylene film was laminated as a protective layer on the surface of the photosensitive resin layer to obtain a photosensitive resin laminate.

<Board>
Resolution evaluation, adhesion evaluation including independent cylinder adhesion, resist pattern skirt evaluation, backlash evaluation of resist pattern sidewall, and surface condition evaluation of resist pattern are Sumitomo Metals with 8 μm copper foil laminated on insulating resin Evaluation was made using Esperflex, Inc.

<Laminate>
While peeling off the protective layer of the photosensitive resin laminate of the present invention, the laminate was laminated at a roll temperature of 105 ° C. with a hot roll laminator (Asahi Kasei Engineering Co., Ltd., AL-70). The air pressure was 0.35 MPa, and the laminating speed was 1.0 m / min.

<Exposure>
After peeling off the support film, a mask film necessary for the evaluation of the photosensitive resin layer was placed on the intermediate layer and exposed with an ultrahigh pressure mercury lamp (OMW Seisakusho, HMW-801) at an exposure amount of 80 mJ / cm ² .

<Development>
A 0.5 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. was sprayed for a predetermined time to dissolve and remove unexposed portions of the photosensitive resin layer. 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. The actual development time was twice as long as the minimum development time to obtain a cured resist pattern.

2. Evaluation method (1) Support film peelability evaluation When the support film was peeled before exposure, the following ranking was given for peelability.
○ (good): Only the support film was peeled off.
Δ (possible): The intermediate layer partially adhered to the support film and peeled off at the same time.
X (impossible): The support film and the intermediate layer were peeled together (peeled between the intermediate layer and the photosensitive resin layer).

(2) Evaluation of resolution Using a line pattern mask having a ratio of 1: 1 of the width of the exposed portion and the unexposed portion as a mask film at the time of exposure for 15 minutes after lamination, as described above, Exposed and developed. The minimum mask width in which the cured resist pattern was normally formed was defined as the resolution value, and the resolution was ranked as follows.
◎ (excellent): The resolution value is 5 μm or less. ○ (good): The resolution value exceeds 5 μm and 10 μm or less. △ (possible): The resolution value exceeds 10 μm and 15 μm or less. Over 15μm

(3) Adhesion evaluation The substrate which had passed 15 minutes after lamination was exposed and developed as described above using a line pattern mask of the exposed portion alone as a mask film at the time of exposure. The minimum mask width in which the cured resist pattern was normally formed was defined as the adhesion value, and the adhesion was ranked as follows.
◎ (excellent): Adhesion value is 5 μm or less ○ (good): Adhesion value exceeds 5 μm and 10 μm or less Δ (possible): Adhesion value exceeds 10 μm and 15 μm or less × (impossible): Adhesion Sex value exceeds 15μm

(4) Evaluation of Independent Cylinder Adhesion The substrate that had passed 15 minutes after lamination was exposed and developed as described above using a cylindrical pattern mask having a single exposed portion as a mask film during exposure. The minimum width of the diameter of the cylindrical mask on which the cured resist pattern was normally formed was defined as the value of the independent cylindrical adhesion, and was ranked as follows.
◎ (excellent): independent cylinder adhesion value is 5 μm or less ○ (good): independent cylinder adhesion value exceeds 5 μm and 10 μm or less △ (possible): independent cylinder adhesion value exceeds 10 μm and 15 μm or less X (impossible): Independent cylinder adhesion value exceeds 15 μm

(5) Suse Evaluation of Resist Pattern Using a chromium glass photomask as a mask film at the time of exposure, the resist pattern was exposed and developed as described above. The shape of the 10 μm line of the obtained cured pattern was ranked according to the following.
A (excellent): The cut portion of the foot of the cured resist is good and there is no sooting.
○ (good): The cut portion of the cured resist has a good cut and minimal pulling.
Δ (possible): Saw pulling of 3 μm or less is observed in the foot portion of the cured resist.
X (impossible): Soo pulling exceeding 3 μm is observed in the foot portion of the cured resist.

(6) Evaluation of Backlash of Side Wall of Resist Pattern The laminated body laminated on the substrate was exposed and developed as described above using a chromium glass photomask. The sidewall shapes of the 10 μm line resist patterns of the obtained cured patterns were ranked according to the following.
○ (good): There is almost no backlash on the formed resist sidewall.
Δ (possible): The resist side wall formed has a slight backlash.
X (impossible): There are rattles at the formed resist sidewalls.

(7) Evaluation of surface state of resist pattern The laminate laminated on the substrate was exposed and developed as described above using a chromium glass photomask. The resist surface states of the 10 μm line of the obtained cured pattern were ranked according to the following.
○ (good): The formed resist surface has almost no dent.
Δ (possible): A very slight depression exists on the formed resist surface.
X (not possible): There are dents on the formed resist surface in some places.

3. Evaluation results The evaluation results of Examples and Comparative Examples are shown in Table 1-1 and Table 1-2. The mass parts of P-1 to P-2 in Table 1-1 and Table 1-2 are amounts including methyl ethyl ketone. In Table 1-1 and Table 1-2, Comparative Example 1 has no intermediate layer, Comparative Example 2 has a thick intermediate layer, and Comparative Example 3 is a compound represented by the general formula (I) in the intermediate layer. Is lacking.

<Symbol explanation>
Q-1: Polyvinyl alcohol (PVA-205 manufactured by Kuraray Co., Ltd.)
Q-2: Polyethylene glycol (weight average molecular weight 400)
Q-3: Polyoxyethylene monomethyl ether (Niox M-550 manufactured by NOF Corporation, weight average molecular weight 550)
Q-4: Polyvinylpyrrolidone (weight average molecular weight 40,000)
P-1: Methyl ethyl ketone solution of binary copolymer of 80% by mass of benzyl methacrylate and 20% by mass of methacrylic acid (solid content concentration 50% by mass, weight average molecular weight 25,000, acid equivalent 430, dispersity 2.7)
P-2: Methyl ethyl ketone solution of ternary copolymer of methyl methacrylate 50 mass%, methacrylic acid 25 mass%, styrene 25 mass% (solid content concentration 35 mass%, weight average molecular weight 50,000, acid equivalent 344, dispersion Degree 3.1)
M-1: Polyalkylene glycol dimethacrylate obtained by adding an average of 3 moles of ethylene oxide to both ends of polypropylene glycol with an average of 12 moles of propylene oxide added M-2: An average of 2 moles of propylene oxide at both ends of bisphenol A Polyalkylene glycol dimethacrylate M-3 with an average of 6 moles of ethylene oxide added: Polyethylene glycol dimethacrylate with an average of 2 moles of ethylene oxide added to each end of bisphenol A 200)
M-4: dimethacrylate of polyethylene glycol with an average of 5 moles of ethylene oxide added to both ends of bisphenol A (NK SL BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.)
M-5: 2,2-bis {4- (methacryloxypentaethoxy) cyclohexyl} propane M-6: reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (Nippon Yushi Co., Ltd., Bremma-PP1000) Urethane polypropylene glycol dimethacrylate M-7: trimethylolpropane trimethacrylate M-8: trioxyethyltrimethylolpropane triacrylate (NK ester A-TMPT-3EO manufactured by Shin-Nakamura Chemical Co., Ltd.)
M-9: Nonaethylene glycol diacrylate G-1: 4,4′-bis (diethylamino) benzophenone G-2: 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer J-1: Diamond green (Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.)
J-2: Leuco Crystal Violet L-1: 1- (2-Di-n-butylaminomethyl) -5-carboxylbenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxylbenzotriazole 1: 1 mixture of L-2: 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid tetraester of pentaerythritol (IRGANOX245 manufactured by Ciba Specialty Chemicals Co., Ltd.)

  The photosensitive resin laminate of the present invention includes a printed wiring board having a conductor pattern, a flexible substrate, a lead frame substrate, a substrate for COF, a substrate for a semiconductor package, and a transparent electrode for liquid crystal and a TFT for liquid crystal as the conductor pattern. It is suitable as an etching resist or a plating resist in the field of manufacturing a substrate having wiring and electrodes for PDP (plasma display panel).

Claims (7)

A support film, and a photosensitive resin laminate comprising, in this order, an intermediate layer and a photosensitive resin layer having a layer thickness of 0.1 μm or more and 10 μm or less on the support film, the intermediate layer comprising polyvinyl alcohol And at least one compound selected from the group consisting of compounds represented by the following general formula (I).
_{R 1 -O- (CH 2 CH 2} O) n 1 -R 2 (I)
(R ₁ and R ₂ are H or CH ₃ , which may be the same or different, and n ₁ is an integer from 3 to 25.)   The photosensitive resin laminate according to claim 1, wherein a protective layer is further laminated on the photosensitive resin layer.   The photosensitive resin layer is (a) a binder resin 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: 20 to 90% by mass, (b) at least one kind of light. It is a layer which consists of a photosensitive resin composition containing the unsaturated compound which can superpose | polymerize: 3-70 mass%, (c) photoinitiator: 0.1-20 mass%. Photosensitive resin laminate.   The photosensitive resin laminate according to claim 3, wherein the (a) binder resin contains benzyl (meth) acrylate as a copolymerization component. The (b) at least one photopolymerizable unsaturated compound is at least one photopolymerizable unsaturated compound selected from the group consisting of compounds represented by the following general formulas (II) to (VI). The photosensitive resin laminated body of Claim 3 or 4.

(In the formula, R ₄ and R ₅ are H or CH ₃ , which may be the same or different, and n ₃ , n ₄ and n ₅ are each independently an integer of 3 to 20) is there.)

Wherein R ₆ and R ₇ are H or CH ₃ , which may be the same or different, A is C ₂ H ₄ , B is CH ₂ CH (CH ₃ ), n ₆ + N ₇ is an integer of 2 to 40, n ₈ + n ₉ is an integer of 0 to 40, n ₆ and n ₇ are each independently an integer of 1 to 39, and n ₈ and n ₉ are each independently 0 to 40 The arrangement of repeating units of-(AO)-and-(B-O)-may be random or block, and in the case of a block,-(AO)-and Any order of-(B-O)-may be on the bisphenyl group side.)

(Wherein R ₈ and R ₉ are H or CH ₃ , which may be the same or different, D is C ₂ H ₄ , E is CH ₂ CH (CH ₃ ), m ₁ + M ₂ is an integer of ₂ to 40, m ₃ + m ₄ is an integer of 0 to 40, m ₁ and m ₂ are each independently an integer of ₁ to 39, and m ₃ and m ₄ are each independently 0 to 40 The arrangement of repeating units of-(DO)-and-(EO)-may be random or block, and in the case of a block,-(DO)-and Any of the order of-(E-O)-may be on the cyclohexyl group side.)

(Wherein R ₁₀ is a divalent organic group having 4 to 12 carbon atoms, R ₁₁ and R ₁₂ are H or CH ₃ , and these may be the same or different. M ₅ and m ₆ is each independently an integer of 1 to 15.)

(In the formula, R ₁₃ is H or CH ₃ , R ₁₄ is an alkyl group having 4 to ₁₄ carbon atoms, A ′ is C ₂ H ₄ , B ′ is CH ₂ CH (CH ₃ ), and m ₇ is 1 to 12. , M ₈ is an integer from 0 to 12, and m ₉ is an integer from 0 to 3. The sequence of repeating units of-(A'-O)-and-(B'-O)-is a block even if it is random. In the case of a block, any of the order of-(A'-O)-and-(B'-O)-may be on the phenyl group side.)   Laminating step of laminating the photosensitive resin laminate according to any one of claims 1 to 5 on the surface of a metal plate or a metal-coated insulating plate, an exposure step of peeling and exposing a support film, unexposed by development A method for forming a resist pattern comprising sequentially developing steps for removing the portions.   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.

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