KR101017550B1 - Photosensitive resin laminate - Google Patents

Abstract

In the photosensitive resin laminate having high characteristics and high adhesion, no splattering on the sidewall of the resist pattern, no depressions on the surface of the resist pattern, and very small sagging after resolution, problems in supporting film peelability It provides a photosensitive resin laminate having no. A photosensitive resin laminate obtained by sequentially laminating an intermediate having a layer thickness of 0.1 µm to 10 µm and a photosensitive resin layer on a supporting film, wherein the intermediate layer contains polyvinyl alcohol and a specific compound. A resin laminate is used.

Description

Photosensitive resin laminated body {PHOTOSENSITIVE RESIN LAMINATE}

The present invention relates to a photosensitive resin laminate and its use. Specifically, a printed wiring board having a conductor pattern, a flexible substrate, a lead frame substrate, a substrate for a chip on film (COF), a substrate for a semiconductor package, and a transparent electrode for a liquid crystal as a conductor pattern, a TFT (Thin for driving a liquid crystal) The photosensitive resin laminated body suitable for manufacture of the board | substrate which has the wiring for film transistors, the electrode for plasma display panels (PDP), the formation method of the resist pattern using the same, and the manufacturing method of a conductor pattern.

In an electronic device, for example, a PC or a mobile telephone, for example, a printed wiring board is used as a board for mounting a component or a semiconductor. As a resist used in order to manufacture a printed wiring board, the photosensitive resin layer which has conventionally laminated | stacked the photosensitive resin layer on a support film, and further laminated | stacked the protective layer on the photosensitive resin layer as needed, what is called a dry film, is mentioned. A resist is used.

As a photosensitive resin layer used here, the thing of alkali developing type which uses weak alkaline aqueous solution as a developing solution is common now.

A general method for producing a printed wiring board using dry film resist is briefly described. First, when there is a protective layer, a protective layer is peeled off. Then, the photosensitive resin layer integrated with a support film is laminated using a laminator for the board | substrate for permanent circuit manufacture, for example, a copper clad laminated board and a flexible board | substrate. Next, exposure is performed through the wiring pattern mask film. The exposure method is diversified according to the use. There is also a method of maskless exposure which does not require a photo mask, for example, direct drawing by a laser. Subsequently, when the support film remains, it is peeled off, and the photosensitive resin layer of the unexposed part is melt | dissolved or disperse | distributed with a developing solution, and the hardened resist pattern (henceforth a resist pattern is abbreviated) is formed on a board | substrate.

After forming the resist pattern, the process of forming the circuit is largely divided into two methods. A 1st method is the method (etching method) of removing the resist pattern part with aqueous alkali solution stronger than a developing solution, after etching away the copper surface of the board | substrate which is not covered by the resist pattern. The second method is a method (plating method) in which the copper surface of the substrate is plated using copper, solder, and nickel, followed by removing the resist pattern portion and etching the copper surface of the substrate again. For etching, a cupric chloride, ferric chloride, copper ammonia complex solution is used.

Moreover, in order to respond to the request of refinement | miniaturization of the conductor pattern of a printed wiring board, the high resolution and adhesiveness of a resist pattern are calculated | required in recent years (patent document 1). The high resolution is generally achieved by improving the crosslinking density of the photosensitive resin composition. When the crosslinking density is improved, the resist pattern after exposure becomes hard and brittle, and part of the resist pattern is removed during the transfer process from the developing process to the etching or plating process. There is a problem of missing. Moreover, especially in the thin film whose film thickness of the photosensitive resin layer is 10 micrometers or less, light may be reflected at the surface of a base material at the time of exposure, and even the photosensitive resin layer which should be unexposed may be photosensitive. The part which has been exposed to light is reflected in the resist pattern, which may cause a short. Moreover, when light is reflected by the surface of a base material at the time of exposure, the development residue that the bottom face of a resist pattern hangs may generate | occur | produce. When sagging occurs, the size may vary depending on the size, but there may be a problem that rattles occur in the copper circuit in the etching process.

Generally as a support film of dry film resist, a polyester film is used. The polyester film contains a trace component, for example a lubricant. This trace component causes a phenomenon that a very minute portion is shielded from light during exposure. As a result of this, there are cases in which a flaw or depression occurs in the sidewall (side wall) of the resist pattern or the surface (surface) facing the substrate in the resist pattern. In particular, in the case of forming a fine wiring having a conductor pattern width of 10 µm or less, this influence cannot be ignored.

As another means of achieving high resolution, a method of forming an intermediate layer made of polyvinyl alcohol between the supporting film and the photosensitive resin layer is known. By peeling a support film and exposing it on an intermediate | middle layer before an exposure process, the influence on the resist pattern shape by the trace component contained in a high resolution and a support film can be excluded. However, when the intermediate layer is formed of polyvinyl alcohol alone, problems may arise in peelability with the support film or solubility in an alkaline developer.

Patent Document 2 discloses a technique for forming an intermediate layer containing polyvinyl alcohol and hydroxyethyl cellulose. However, in this technique, it is very difficult to control the peelability of a film between a support film and an intermediate | middle layer, and research is needed for an intermediate | middle layer composition.

In patent document 3, the technique in which the oxypropylene group containing polyvinyl alcohol-type resin is used for an intermediate | middle layer, and the (meth) acrylic acid partial ester of polyhydric alcohol is shown in the photosensitive resin layer. Patent document 4 has an intermediate layer whose main component is at least 1 type selected from the group which consists of polyvinyl alcohol which copolymerized a specific amount of olefin, polyethylene oxide of 4000 degree or more of polymerization degree, a carboxyl group-containing acrylate resin, and a copolymer of dibasic acid and an olefin. Although the technique is disclosed, these methods have not solved the problem of sagging of the resist pattern after high resolution, high adhesion, and development.

The production of a printed wiring board having a fine conductor pattern, the production of a C0F substrate requiring a high resolution and a thin film, and the production of a substrate for a semiconductor package exhibit high resolution, and a rattling of the sidewall in the shape of a resist pattern after development. There has been a demand for a photosensitive resin composition and a photosensitive resin laminate in which the surface is free of depressions, and the sagging after development is very small.

Patent Document 1: Japanese Patent Application Laid-Open No. 2001-159817

Patent Document 2: Japanese Patent Application Laid-Open No. 63-197942

Patent document 3: Unexamined-Japanese-Patent No. 4-371957

Patent document 4: Unexamined-Japanese-Patent No. 6-242611

DISCLOSURE OF INVENTION

Problems to be Solved by the Invention

The present invention provides a support film as a photosensitive resin laminate, which exhibits high resolution and high adhesion, has no splattering on the sidewall of the resist pattern, no depression on the surface of the resist pattern, and has a very small sagging after development. It aims at providing the photosensitive resin laminated body which does not have a problem in peelability, the formation method of the resist pattern using this laminated body, and the manufacturing method of a conductor pattern.

Means to solve the problem

MEANS TO SOLVE THE PROBLEM As a result of examining in order to solve the said subject, by using a specific photosensitive resin laminated body, there existed no problem in the peelability of a support film, and after image development, it expressed high resolution and high adhesiveness, and was loosened to the sidewall of a resist pattern. It has been found that it is possible to provide a photosensitive resin laminate which has no roughness, no depression on the surface of the resist pattern, and very small sagging after development, and has thus reached the present invention.

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, in this order, an intermediate layer having a layer thickness of 0.1 µm to 10 µm and a photosensitive resin layer on the supporting film and the supporting film, wherein the intermediate layer is polyvinyl alcohol and the following general formula ( Said photosensitive resin laminated body containing 1 or more types of compounds chosen from the group which consists of a compound represented by I).

R ₁ -O- (CH ₂ CH ₂ O) n ₁ -R ₂ (I)

(R ₁ and R ₂ Is H or CH ₃ , these may be the same or different, n ₁ is an integer of 3 to 25)

(2) The photosensitive resin laminated body as described in (1) which laminates a protective layer further on the said photosensitive resin layer.

(3) Resin for binders whose said photosensitive resin layer is (a) carboxyl group content is 100-600 in acid equivalent, and a weight average molecular weight is 5000-50000: 20-90 mass%, (b) At least 1 sort (s) of photopolymerization is possible Unsaturated compound: 3-70 mass%, (c) Photoinitiator: The photosensitive resin laminated body as described in (1) or (2) which is a layer which consists of a photosensitive resin composition containing 0.1-20 mass%.

(4) Photosensitive resin laminated body as described in (3) in which said resin for binder (a) contains benzyl (meth) acrylate as a copolymerization component.

(5) (3) or (4) wherein (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): Photosensitive resin laminated body of description.

[Formula 1]

(Wherein, R ₄ and R ₅ are H or CH ₃ , which may be the same or different, and n ₂ , n ₃ and n ₄ are each independently an integer of 3 to 20)

[Formula 2]

(Wherein R ₆ and R ₇ are H or CH ₃ , these 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 from 2 to 40, n _{8 9} + n is an integer of 0 to 40, n ₆ and n ₇ is 1 to 39 are each independently an integer, n ₈ and n ₉ are each independently an integer from 0 to 40. The arrangement of repeating units of-(AO)-and-(BO)-may be random or block. In the case of blocks, the order of-(AO)-and-(BO)-may be the bisphenyl group side)

(3)

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 ~ 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 an integer of 0 to 40. The arrangement of the repeating units of-(DO)-and-(EO)-may be random or block. In the case of a block, the order of-(DO)-and-(EO)-may be one of the cyclohexyl group side)

[Formula 4]

(Wherein, R ₁₀ are carbon atoms, a divalent organic group, R ₁₁ and R ₁₂ of 4 to 12 is H or CH _3, which may be the same or different. M ₅ and m ₆ is from 1 to 15 are each independently Is an integer)

[Chemical Formula 5]

(Wherein 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 ), m ₇ is 1-12, m ₈ Is 0-12 and m ₉ is an integer of 0 to 3. The array of repeating units of-(A'-O)-and-(B'-O)-may be random or a block. The order of A'-O)-and-(B'-O)-may be the phenyl group side)

(6) The unexposed part by the lamination process of laminating the photosensitive resin laminated body in any one of (1)-(5) to the surface of a metal plate or a metal clad insulation board, the exposure process which peels and exposes a support film, and develops. A method of forming a resist pattern comprising a developing step of removing in order.

(7) The method of manufacturing a conductor pattern, wherein the substrate on which the resist pattern is formed is etched or plated by the method described in (6).

Effects of the Invention

According to the present invention, there is no problem in the peelability of the support film, and after development, it exhibits high resolution and high adhesiveness, there is no splattering on the sidewall of the resist pattern, no depression on the surface of the resist pattern, and sagging after development is very high. Providing a small photosensitive resin laminated body, the formation method of the resist pattern using this laminated body, and the manufacturing method of a conductor pattern can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of the photosensitive resin laminated body of this invention (the said (1) item).

Fig. 2 is a schematic diagram of the photosensitive resin laminate of the present invention (above (2)). Explanation of the sign

1 support film

2 mezzanine

3 photosensitive resin layer

4 protective layer

Carrying out the invention  Best form for

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely.

The photosensitive resin laminated body of this invention is a photosensitive resin laminated body formed by laminating | stacking the intermediate | middle layer and photosensitive resin layer which layer thickness is 0.1 micrometer-10 micrometers sequentially on a support film.

The photosensitive resin laminated body of this invention is characterized in that the intermediate | middle layer contains polyvinyl alcohol and 1 or more types of compounds chosen from the group which consists of a compound represented by 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 , these may be the same or different, n ₁ is an integer of 3 to 25)

As a compounding weight ratio in the intermediate | middle layer of polyvinyl alcohol, it is preferable that they are 50 mass% or more and 95 mass% or less from a viewpoint of developability and cost. More preferably, they are 70 mass% or more, More preferably, they are 75 mass% or more and 90 mass% or less.

As a compounding weight ratio in the intermediate | middle layer of the compound of General formula (I), 5 mass% or more and 50 mass% or less are preferable from a peelable viewpoint of a support film and an intermediate layer, More preferably, they are 5 mass% or more and 30 mass% or less. More preferably, they are 5 mass% or more and 15 mass% or less.

Polyvinyl alcohol is generally produced by alkali saponification of polyvinyl acetate. As for the weight average molecular weight of the polyvinyl alcohol used for this invention, 1,000-100,000 are preferable. More preferable weight average molecular weights are 5,000-50,000 from an oxygen barrier property and developability. Moreover, as for saponification degree, 50 mol% or more is preferable from a developable viewpoint, Preferably it is 70 mol% or more, More preferably, it is 80 mol% or more.

The weight average molecular weight of the polyvinyl alcohol used for the photosensitive resin laminate of the present invention is gel permeation chromatography (GPC) manufactured by Nippon Spectro Co., Ltd. (pump: Gulliver, PU-1580 type, column: Showa Electric Co., Ltd.) It is calculated | required as a weight average molecular weight (polystyrene conversion) by Shodex (trademark) (HFIP-805, HFIP-803) of 2 production lines, a moving bed solvent: hexafluoroisopropanol, and a calibration curve by a polystyrene standard sample.

As for the compound represented by the said General formula (I), n <_1> is preferable at least 3 from a viewpoint of a bad smell, and n <_1> is 25 or less from a viewpoint of compatibility and developability with polyvinyl alcohol. n ₁ becomes like this. More preferably, it is 5 or more and 20 or less, More preferably, it is 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 (PEG200 manufactured by Nippon Oil and Fats Co., Ltd.), polyethylene glycol having an average molecular weight of 300 (PEG300 of Nippon Oil and Fats Co., Ltd., polyethylene glycol having an average molecular weight of 400). (PEG400 manufactured by Nippon Oil Holding Co., Ltd.), polyethylene glycol having an average molecular weight of 600 (PEG600 produced by Nippon Oil Holding Co., Ltd.), polyethylene glycol having an average molecular weight of 1000 (PEG1000 produced by Nippon Oil Holding Co., Ltd.) or polyethylene glycol monomethyl ether having an average molecular weight of 400 (Nippon Oil Holding Uniox M-400 manufactured by Co., Ltd., polyethylene glycol monomethyl ether having an average molecular weight of 550 (Niox M-550 manufactured by Nippon Oil Holding Co., Ltd.), polyethylene glycol monomethyl ether having an average molecular weight of 1000 (Unox M-1000 manufactured by Nippon Oil Corporation) )

Moreover, you may add a well-known water-soluble polymer other than the above to an intermediate | middle layer. Specific examples of the water-soluble polymers 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. As a specific example of polyvinylpyrrolidone, K-15 with a weight average molecular weight of 40,000 by Nippon Shokubai Co., Ltd., K-30 with a weight average molecular weight of 100,000, K-85 with a weight average molecular weight of 900,000, and a weight average molecular weight of 1,000,000 There is K-90.

As for the layer thickness of an intermediate | middle layer, 10 micrometers or less are preferable from a viewpoint of a resolution, adhesiveness, and developability, More preferably, it is 5 micrometers or less, More preferably, it is 3 micrometers or less. Moreover, it is 0.1 micrometer or more from a viewpoint of oxygen barrier property, Preferably it is 0.5 micrometer or more, More preferably, it is 1 micrometer or more.

In this invention, peeling a support film before exposure is preferable in achieving high resolution. When peeling a support film before exposure, a support film may be transparent or an opaque one which transmits exposure light. As a support film in this invention, there exists a synthetic resin film represented by polyethylene, a polypropylene, a polycarbonate, polyethylene terephthalate of 10 micrometers-100 micrometers in thickness. Usually, polyethylene terephthalate having suitable flexibility and strength is preferably used. In order to prevent wrinkles from occurring during lamination and to prevent breakage of the support film, the film thickness is preferably 10 µm or more.

The photosensitive resin laminated body of this invention is excellent in the peelability of a support film because an intermediate | middle layer employ | adopts the said structure. That is, when peeling a support film before an exposure process, the interlayer adhesive force of a support film and an intermediate | middle layer is a photosensitive resin laminated body lower than an intermediate | middle layer and the photosensitive resin layer.

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

As a characteristic of a protective layer, it is important that the interlayer adhesive force between the photosensitive resin layer and a protective layer is lower than the interlayer adhesive force between a support film and an intermediate | middle layer, and can easily peel a protective layer at the time of lamination by this.

As a protective layer, there exists a synthetic resin film represented by polyethylene, a polypropylene, a polycarbonate, polyethylene terephthalate of 10-100 micrometers thick. Especially, a polyethylene film or a polypropylene film is used preferably.

100 micrometers or less are preferable, as for the upper limit of the film thickness of the photosensitive resin layer of this invention, 50 micrometers or less are more preferable, 30 micrometers or less are more preferable, and 10 micrometers or less are the most preferable. 0.5 micrometer or more is preferable and, as for the minimum of a film thickness, 1 micrometer or more is preferable.

The photosensitive resin layer in the photosensitive resin laminated body of this invention is (a) resin for binders whose carboxyl group content is 100-600 in acid equivalent, and a weight average molecular weight is 5000-50000: 20-90 mass%, (b) at least It is preferable that it is a layer which consists of a photosensitive resin composition containing 1 type of photopolymerizable unsaturated compounds: 3-70 mass% and (c) photoinitiator: 0.1-20 mass%.

The photosensitive resin composition used for the photosensitive resin laminated body of this invention is demonstrated in detail below.

(a) As for the quantity of the carboxyl group contained in resin for binders, 100-600 are preferable in acid equivalent, More preferably, it is 250-450, More preferably, it is 300-450. An acid equivalent means the mass of resin for binder which has a 1 equivalent carboxyl group in it.

The carboxyl group in resin for binders is necessary in order to provide developability and peelability with respect to aqueous alkali solution to the photosensitive resin layer. The acid equivalent is preferably 100 or more from the viewpoint of development resistance, resolution and adhesion, and preferably 600 or less from the viewpoint of developability and peelability.

(a) It is preferable that the weight average molecular weights of resin for binders are 5,000-500,000. As for the weight average molecular weight of resin for binders, 500,000 or less are preferable from a viewpoint of resolution, and 5000 or more are preferable from a viewpoint of an edge fuse. In order to exhibit the effect of this invention better, it is more preferable that the weight average molecular weights of resin for binders are 5,000-200,000, More preferably, it is 5,000-100,000. Dispersion degree (it may be called molecular weight distribution) is represented by the ratio of the weight average molecular weight and number average molecular weight of the following formula.

(Dispersity) = (weight average molecular weight) / (number average molecular weight).

As for dispersion degree, the thing of about 1-6 is used, Preferably it is 1-4.

In addition, the measurement of acid equivalent is performed by potentiometric titration method using 0.1 mol / L sodium hydroxide aqueous solution using Hiranuma automatic titration apparatus (COM-555) by Hiranuma Industries.

Molecular weight is gel permeation chromatography (GPC) manufactured by Nippon Spectroscopy Co., Ltd. (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko Co., Ltd.) (KF-807, KF-806M, KF-806M, KF-802.5) Four in-line, moving bed solvent: tetrahydrofuran, weight average molecular weight and number by polystyrene standard sample (using calibration curve by Shodex STANDARD SM-105 manufactured by Showa Electric Co., Ltd.) Average molecular weight (polystyrene equivalent) is obtained.

(a) Resin for binders is obtained by copolymerizing 1 type or more of monomers among the following 2 types of monomers, respectively.

The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. For example, (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid semiester are mentioned. Especially, (meth) acrylic acid is preferable. Here, (meth) acryl represents acryl and methacryl. It is the same below.

The second monomer is non-acidic and is a compound having one polymerizable unsaturated group in the molecule. The compound is selected to maintain 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, and 2-hydroxy. Ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylonitrile, benzyl (meth) acrylate, methoxybenzyl (meth) acrylate, chlorobenzyl (meth) acrylate, green Furyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, cresyl (meth) acrylate, naphthyl (meth) acrylate, phenyl group Vinyl compounds (for example, styrene) having In particular, benzyl (meth) acrylate is preferable from the viewpoint of resolution and developer cohesion.

(a) The binder resin is a radical polymerization initiator such as benzoyl peroxide or azoisobutyro in 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 | combine by adding an appropriate amount of nitrile and stirring with overheating. In some cases, synthesis is carried out while dropping a part of the mixture into the reaction solution. After completion | finish of reaction, a solvent may be further added and it may adjust to desired density | concentration. In addition to solution polymerization, block polymerization, suspension polymerization, or emulsion polymerization may be used as the synthesis means.

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

(b) As at least 1 type of photopolymerizable unsaturated compound, at least 1 type of photopolymerizable unsaturated compound chosen from the group which consists of a compound represented by following General formula (II)-(VI) from a high resolution viewpoint is used for the photosensitive resin composition. It is a preferred embodiment to do so.

[Formula 6]

(Wherein, R ₄ and R ₅ are H or CH ₃ , which may be the same or different, and n ₂ , n ₃ and n ₄ are each independently an integer of 3 to 20)

[Formula 7]

(Wherein R ₆ and R ₇ are H or CH ₃ , these 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 from 2 to 40, n ₈ + n ₉ is an integer from 0 to 40, n ₆ And n ₇ Are each independently an integer from 1 to 39, n ₈ And n <_9> is an integer of 0-40 each independently. The arrangement of repeating units of-(AO)-and-(BO)-may be random or block. In the case of blocks, the order of-(AO)-and-(BO)-may be the bisphenyl group side)

[Formula 8]

In which R ₈ and R ₉ Is H or CH ₃ , these 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 2-40, m ₃ + m ₄ is of 0 to 40 integer, m ₁ and m ₂ are each independently an integer of 1 ~ 39, m ₃ and m ₄ are each independently an integer from 0 to 40. The arrangement of the repeating units of-(DO)-and-(EO)-may be random or block. In the case of a block, the order of-(DO)-and-(EO)-may be one of the cyclohexyl group side)

[Formula 9]

(In formula, R <_10> is a C4-C12 divalent organic group, R <_11> and R <_12>. Is H or CH ₃ , and these may be the same or different. m ₅ and m ₆ are each independently an integer of 1 to 15)

[Formula 10]

Wherein 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 ), m ₇ is 1-12, m ₈ is 0-12, m ₉ is an integer of 0-3. . The arrangement of repeating units of-(A'-O)-and-(B'-O)-may be random or block. In the case of a block, the order of-(A'-O)-and-(B'-O)-may be either phenyl group side)

It is preferable that n <_2> , n <_3> and n <_4> are three or more from a boiling point and a bad smell from the compound represented by the said General formula (II). It is n _2, n ₃ and n ₄ is not more than 20 in view of the sensitivity resulting from the concentration of the optically active area per unit weight are preferred. As a specific example of the compound represented by the said General formula (II) used for this invention, For example, Glycol which added 3 mol of ethylene oxide to both ends on the both ends of the polypropylene glycol which added the average of 12 mol of propylene oxide, respectively. Dimethacrylate of is mentioned as a preferable thing.

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 when it exceeds 40, it is not preferable from the viewpoint of sensitivity. Preferably it is 30 or less.

As a specific example of the compound represented by the said General formula (III) used for this invention, the dimethacryl of polyalkylene glycol which added an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide to both ends of bisphenol A, respectively. Polyethylene having an average of 5 moles of ethylene oxide added to both ends of the dimethacrylate bisphenol A of polyalkylene glycols each having an average of 2 moles of propylene oxide and an average of 15 moles of ethylene oxide added to both ends of bisphenol A. Dimethacrylate of glycol (the NK ester BPE-500 by Shin-Nakamura Chemical Industry Co., Ltd.) and bisphenol A of polyethylene glycol which added an average of 2 mol of ethylene oxide to both ends of glycol (Shin-Nakamura Chemical Industries Co., Ltd.). NK ester BPE-200 by the company.

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 when it exceeds 40, it 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. The polyethyleneoxy group which the compound has has monoethyleneoxy group, diethyleneoxy group, triethyleneoxy group, tetraethyleneoxy group, pentaethyleneoxy group, hexaethyleneoxy group, heptaethyleneoxy group, octaethyleneoxy group, nonaethylene jade The compound of any one group chosen from the group which consists of time period, a decaethyleneoxy group, an undecaethyleneoxy group, a dodecaethyleneoxy group, a tridecaethyleneoxy group, a tetradecaethyleneoxy group, and a pentadecaethyleneoxy group is preferable. Moreover, 2, 2-bis {(4-acryloxy polyoxy) cyclohexyl} propane or 2, 2-bis {(4-methacryloxy polyalkylene oxy) cyclohexyl} propane is also mentioned. As a polyalkylene oxy group which the compound has, the mixture of an ethyleneoxy group and a propyleneoxy group is mentioned, The addition product of the block structure of an octaethyleneoxy group and a dipropyleneoxy group, or the addition product of a random structure, and tetraethyleneoxy group and a tetrapropylene Additives of the block structure of the oxy group or the addition of the random structure, the addition of the block structure of the pentadecaethyleneoxy group and the dipropyleneoxy group, or the addition of the random structure are preferable. Of these, 2,2-bis {(4-methacryloxypentaethyleneoxy) cyclohexyl} propane is most preferred.

In the compound represented by the general formula (V), sufficient sensitivity is not obtained when m ₅ or m ₆ exceeds 15. In formula, R <_10> is a C4-C12 divalent organic group and is a residue of diisocyanate.

As a specific example of the compound represented by the said General formula (V), a diisocyanate compound, for example, hexamethylene diisocyanate, tolylene diisocyanate, or 2,2,4-trimethylhexamethylene diisocyanate, and a hydroxide in 1 molecule The compound which has a real group and a (meth) acryl group, for example, the urethane compound of 2-hydroxypropyl acrylate and oligopropylene glycol monomethacrylate is mentioned. Specifically, there is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (manufactured by Nippon Oils & Fats, Inc., Brenmer PP1000).

A compound represented by the general formula (Ⅵ) is not a sufficient sensitivity is not obtained when the m ₇ m ₈ or greater than 12. Even if m ₉ exceeds 3, sufficient sensitivity cannot be obtained.

As a specific example of the compound represented by the said General formula (VI), For example, the polypropylene glycol which added an average of 2 mol of propylene oxide, and the polyethylene glycol which added an average of 7 mol of ethylene oxide to the nonylphenol of the compound The 4-normal nonyl phenoxy heptaethylene glycol dipropylene glycol acrylate which is an acrylate is mentioned. 4-normal nonyl phenoxy octaethylene glycol acrylate (The Toa Synthetic Co., Ltd. product, M-114) which is an acrylate of the compound which added the polyethyleneglycol which added an average of 8 mol ethylene oxide to nonylphenol is also mentioned.

(b) As a compound which does not belong to the group which consists of a compound represented by said general formula (III), (IV), (V), (VI) and (iii) which is at least 1 type of photopolymerizable unsaturated compound, There is a photopolymerizable unsaturated compound shown. For example, 1, 6- hexanediol di (meth) acrylate, 1, 4- cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethyleneglycol di (meth) acrylate, 2 -Di (p-hydroxyphenyl) propanedi (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxy Ethyl trimethylol propane triacrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropanetriglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether Di (meth) acrylate, β-hydroxypropyl-β '-(acryloylkishi) propylphthalate, phenoxypolyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) a Acrylate.

The ratio with respect to the whole photosensitive resin composition of the at least 1 sort (s) of photopolymerizable unsaturated compound chosen from the group which consists of a compound represented by said general formula (II)-(VI) is 3-70 mass%. It is 3 mass% or more from a viewpoint of a resolution, and is 70 mass% or less from a flexible viewpoint of a resist pattern. More preferably, it is 3-30 mass% or less.

(b) As for the ratio with respect to the whole photosensitive resin composition of the whole photopolymerizable unsaturated compound, 3 mass% or more is preferable from a viewpoint of a sensitivity, and 70 mass% or less is preferable from an viewpoint of an edge fuse. More preferably, it is 10-60 mass%, More preferably, it is 15-55 mass%.

As a (c) photoinitiator, what is necessary is just a compound which is activated by various actinic rays, for example, an ultraviolet-ray, and (b) initiates superposition | polymerization of the unsaturated compound which can be photopolymerized, and is represented by the following general formula (i) The use of triarylimidazole dimers is a preferred embodiment in view of high resolution.

[Formula 11]

(Wherein, X, Y, and Z each independently represents any one of hydrogen, an alkyl group, an alkoxy group, and a halogen group, and p, q, and r each independently represent an integer of 1 to 5).

In the triarylimidazole dimer represented by the said general formula (i), the covalent bond which couples two ropin groups is 1,1'-, 1,2'-, 1,4'-, 2,2 ' -, 2,4'- or 4,4'- bond and the like, wherein the compound of the general formula (VII) whose covalent bond is a 1,1'- bond is preferred. Examples of the 2,4,5-triarylimidazole dimer include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-bis- (m-methoxyphenyl) imidazole dimer, 2- (p-methosikiphenyl) -4,5-diphenylimidazole dimer, especially 2- (o-chlorophenyl) Preference is given to -4,5-diphenylimidazole dimers.

As a (c) photoinitiator used for this invention, the system which uses together the 2,4,5-triaryl imidazole dimer and p-aminophenyl ketone represented by the said General formula (i) is preferable. As p-aminophenyl ketone, p-amino benzophenone, p-butylamino acetophenone, p-dimethylamino acetophenone, p-dimethylamino benzophenone, p, p'-bis (ethylamino) benzophenone, for example , p, p'-bis (dimethylamino) benzophenone [mihilerketone], p, p'bis (diethylamino) benzophenone and p, p'-bis (dibutylamino) benzophenone.

Moreover, photoinitiators other than the compound shown above are quinones, for example, 2-ethyl anthraquinone and 2-tert- butyl anthraquinone. Benzoin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, acridine compounds such as 9-phenylacridine, else benzyldimethyl ketal, benzyldiethyl ketal. There is also a combination of thioxanthones such as thioxanthone, 2,4-diethyl thioxanthone and 2-chlorothioxanthone and a tertiary amine compound such as a dimethylaminobenzoic acid alkyl ester compound. . Moreover, oxime esters, for example, 1-phenyl-1,2-propanedione-2-O-benzoyl oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime have. Moreover, an N-aryl- (alpha)-amino acid compound can also be used, Among these, N-phenylglycine is especially preferable.

It is preferable that the photosensitive resin composition in the photosensitive resin laminated body of this invention contains 0.1-20 mass% of (c) photoinitiators with respect to the whole photosensitive resin composition. From a viewpoint of obtaining sufficient sensitivity, 20 mass% or less is preferable from a viewpoint of preventing light from reflecting off a surface of a base material at the time of exposure and 0.1 mass%.

A basic dye can be used as the photosensitive resin composition. Specific examples of the basic dye include fuchsin, phthalocyanine green, auramin base, chalcoxide green S, crystal violet, methyl orange, nile blue 2B, malachite green (Hodogaya Chemical Co., Ltd.) ) MALACHITE GREEN), basic blue 20, diamond green (Higen (registered trademark) manufactured by Hodogaya Chemical Co., Ltd.) DIAMOND GREEN GH), Victoria Blue (Izen (registered trademark) manufactured by Hodogaya Chemical Co., Ltd.) VICTORIA PURE BLUE) Can be mentioned.

The photosensitive resin composition may also contain a color-based dye developed by light irradiation. As a chromophore dye used, there exists a combination of a leuco dye and a halogen compound, for example. Examples of the leuco dyes include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet] and tris (4-dimethylamino-2-methylphenyl) methane [leuco malachite green].

Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutyl bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, and tris (2,3-dibromopropyl Phosphate, trichloroacetoamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, and halogenated triazine compounds. As the halogenated triazine compound, 2,4,6-tris (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

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.

As for content in the case of containing basic dye and leuco dye, 0.01-10 mass% is preferable in the photosensitive resin composition, respectively. 10 mass% or less is preferable at the point which can confirm sufficient coloring (chromic property) from 0.01 mass% or more, the point which has contrast of an exposure part and an unexposed part, and hold | maintain storage stability.

Moreover, in order to improve the thermal stability and storage stability of the photosensitive resin composition of this invention, it is preferable to contain a radical polymerization inhibitor and benzotriazole in a photosensitive resin composition.

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

Moreover, as benzotriazole, 1, 2-, 3- benzotriazole, 1-chloro- 1,2, 3- benzotriazole, bis (N-2-ethylhexyl) amino methylene- 1, 2, 3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1, 1,2,3-benzotriazole Can be mentioned. Moreover, as carboxy benzotriazoles, 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N- (N, N-di-2- Ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzo Triazoles.

The total addition amount of each of the radical polymerization inhibitor and the benzotriazoles is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass. 0.01 mass% or more is preferable from a viewpoint of providing storage stability to the photosensitive resin composition, and 3 mass% or less is more preferable from a viewpoint of maintaining light sensitivity.

These radical polymerization inhibitors and benzotriazole compounds may be used independently and may be used together 2 or more types.

Moreover, you may contain a plasticizer in the photosensitive resin composition as needed. Such plasticizers include phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, triethyl citrate, acetyl citrate tri-n-propyl, acetyl Citric acid tri-n-butyl, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether. As content in the case of containing a plasticizer, 5-50 mass% is preferable in the photosensitive resin composition, More preferably, it is 5-30 mass%. 5 mass% or more is preferable from a viewpoint of suppressing delay of image development time, or providing flexibility to a cured film, and 50 mass% or less is preferable from a viewpoint of suppressing hardening shortage or cold flow.

Hereinafter, with reference to FIG. 1 and FIG. 2, the support film 1, the intermediate | middle layer 2, the photosensitive resin layer 3, and the protective layer 4 are laminated | stacked sequentially as needed, and the method of manufacturing the photosensitive resin laminated body is shown. Describe.

First, a polyvinyl alcohol, for example, the solid content ratio becomes 5-30 weight% of 1 or more types of compounds chosen from the group which consists of PVA-205 resin by Kuraray Co., Ltd., and the compound represented by the said General formula (I). The amount is gradually added to water heated to 60 to 90 ° C., stirred for about 1 hour, and uniformly dissolved to obtain a uniform aqueous solution of the intermediate layer composition. It is preferable to adjust the viscosity of the uniform aqueous solution of the intermediate | middle layer composition containing polyvinyl alcohol to 10-500 mPa * s. Subsequently, this aqueous solution is apply | coated on a support film 1 using a bar coater or a roll coater, and it dries, and the support film 1 in which the intermediate | middle layer 2 was formed is obtained.

Separately, the combination liquid of the photosensitive resin composition is manufactured. It is preferable to add a solvent so that the viscosity of the preparation liquid of the photosensitive resin composition may be 500-4000 mPa * sec at 25 degreeC. Examples of the solvent used may include ketones and alcohols such as methyl ethyl ketone (MEK), for example methanol, ethanol, and isopropyl alcohol.

The photosensitive resin layer 3 which consists of the photosensitive resin composition on the intermediate | middle layer of the support film 1 in which the intermediate | middle layer 2 was formed is apply | coated and dried using a bar coater or a roll coater similarly to application | coating of the intermediate | middle layer 2.

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

Next, an example of the method of manufacturing a printed wiring board using the photosensitive resin laminated body of this invention is demonstrated.

A printed wiring board is manufactured through each of the following processes.

(1) Lamination Process

When a photosensitive resin laminated body has a protective layer, the process of making it adhere | attach on a board | substrate, for example, a copper clad laminated board or a flexible board | substrate, using a hot roll laminator, peeling a protective layer.

(2) exposure process

The process of peeling a support film from the photosensitive resin laminated body, adhering the mask film which has a desired wiring pattern on an intermediate | middle layer, and exposing using an active light source.

(3) developing process

Process of melt | dissolving or disperse | distributing the unexposed part of an intermediate | middle layer and the photosensitive resin layer using alkaline developing solution, and forming a hardening resist pattern on a board | substrate.

(4) etching process or plating process

Etching liquid is sprayed on the formed resist pattern, and the process of etching the copper surface which is not covered by the resist pattern, or the process of performing plating process represented by copper, solder, nickel, and tin on the copper surface which is not covered by a resist pattern. Thereby, a conductor pattern can be manufactured.

(5) peeling process

Process of removing a resist pattern from a board | substrate using alkali peeling liquid.

As an active light source used in said (2) exposure process, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, a xenon lamp is mentioned, for example. Moreover, in order to obtain a finer resist pattern, it is more preferable to use a parallel light source. In order to minimize the influence of dust and foreign substances, exposure (proxy exposure) may be performed in a state where the photomask is floated from several tens of micrometers to several hundred micrometers or less from the support film.

Moreover, the aqueous solution of sodium carbonate or potassium carbonate is mentioned as alkaline developing solution used at said (3) image development process. Although these aqueous alkali solution is selected according to the characteristic of the photosensitive resin layer, generally 0.5 mass% or more and 3 mass% or less sodium carbonate aqueous solution is used.

The said (4) etching process is performed by acidic etching and alkali etching, for example. The method suitable for the dry film resist to use these is selected.

As the alkaline stripping solution used in the above (5) stripping step, an alkaline aqueous solution that is generally stronger than the aqueous alkaline solution used in development, for example, an aqueous solution of sodium hydroxide or potassium hydroxide of 1% by mass or more and 5% by mass or less. Can be mentioned.

Moreover, when a plating process is selected, after peeling a resist pattern, the copper surface exposed under the resist pattern may be further etched.

Hereinafter, the example of embodiment of this invention is demonstrated in detail by an Example.

Below, the preparation method of the sample for evaluation of an Example and a comparative example, the evaluation method, and the evaluation result about the obtained sample are shown.

[Examples 1 to 12] and [Examples 1 to 3]

1. Preparation of Samples for Evaluation

The photosensitive resin laminated body in an Example and a comparative example was produced as follows.

<Production of Photosensitive Resin Laminate>

First, the intermediate layer compositions shown in Tables 1-1 and 1-2 were gradually added to water heated to 85 ° C so as to have a solid content ratio of 10% by mass, stirred for about 1 hour, and uniformly dissolved to uniformly dissolve the intermediate layer composition. An aqueous solution was obtained. A 16 µm thick polyethylene terephthalate film was used as the supporting film, and the aqueous solution was applied onto the supporting film using a bar coater. Subsequently, it dried for 3 minutes in the dryer of 100 degreeC, and formed the uniform intermediate | middle layer on the support film. The thickness of the intermediate layer was 2 micrometers. On the intermediate | middle layer laminated | stacked on the support film, the photosensitive resin composition shown in Table 1-1 and Table 1-2 was apply | coated uniformly using a bar coater, it dried in a 95 degreeC dryer for 3 minutes, and the uniform photosensitive resin layer was Formed. The thickness of the photosensitive resin layer was 3 micrometers.

Subsequently, a 25 micrometer-thick polyethylene film was stuck as a protective layer on the surface on the photosensitive resin layer, and the photosensitive resin laminated body was obtained.

<Substrate>

Resolution evaluation, adhesion evaluation including independent circumferential adhesion, lagging evaluation of resist pattern, lagging evaluation of sidewall of resist pattern, and surface condition evaluation of resist pattern were sumitomo metal laminated 8 µm copper foil on insulating resin. It evaluated using the Sperflex Co., Ltd. make.

<Laminate>

It laminated at the roll temperature of 105 degreeC by the hot roll laminator (Asahi Kasei Engineering Co., Ltd. product, AL-70), peeling the protective layer of the photosensitive resin laminated body of this invention. The air pressure was 0.35 MPa, and the lamination speed was 1.0 m / min.

<Exposure>

After peeling a support film, the mask film required for evaluation of the photosensitive resin layer was put on the intermediate | middle layer, and it exposed at the exposure amount of 80mJ / cm <2> by the ultrahigh pressure mercury lamp (HMW-801 make).

<Phenomena>

Given a 0.5 mass% Na ₂ CO ₃ aqueous solution for 30 ℃ time it was sprayed, and dissolve and remove the unexposed portion of the photosensitive resin layer. At this time, the minimum time required for the photosensitive resin layer of the unexposed part to melt | dissolve completely was made into the minimum developing time. The actual development time was developed at twice the minimum development time to obtain a cured resist pattern.

2. Evaluation method

(1) evaluation of support film peelability

When peeling a support film before exposure, the grade was divided as follows regarding peelability.

○ (good): Only the support film was peeled off.

△ (possible): Some intermediate layer was attached to the supporting film and peeled at the same time.

X (impossible): The support film and the intermediate | middle layer peeled together (it peeled between an intermediate | middle layer and the photosensitive resin layer).

(2) resolution evaluation

The board | substrate which passed 15 minutes after lamination was exposed and developed as above using the line pattern mask whose width | variety of an exposure part and an unexposed part is 1: 1 as a mask film at the time of exposure. The minimum mask width in which the cured resist pattern was normally formed was regarded as the resolution value, and the resolution was divided as follows.

◎ (excellent): The value of resolution is 5 탆 or less

○ (good): The value of resolution exceeds 5 micrometers and is 10 micrometers or less

△ (possible): The value of the resolution exceeds 10 μm, and 15 μm or less

× (impossible): The value of resolution exceeds 15 µm

(3) adhesion evaluation

The board | substrate which passed 15 minutes after lamination was exposed and developed as mentioned above using the line pattern mask of an exposure part alone as a mask film at the time of exposure. The minimum mask width in which the cured resist pattern was normally formed was made into an adhesive value, and adhesiveness was divided as follows.

◎ (excellent): adhesion value is 5 μm or less

○ (good): Adhesive value exceeds 5 micrometers and is 10 micrometers or less

△ (possible): adhesiveness value exceeds 10 micrometers and 15 micrometers or less

× (impossible): The adhesive value exceeds 15 μm

(4) Independent circumferential adhesion evaluation

The board | substrate which passed 15 minutes after lamination was exposed and developed as mentioned above using the circumferential pattern mask of an exposure part only as a mask film at the time of exposure. The minimum width | variety of the circumferential mask diameter in which the hardening resist pattern is normally formed was made into the value of independent circumferential adhesiveness, and it divided into grades as follows.

◎ (excellent): value of independent circumferential adhesion is 5 μm or less

○ (good): The value of independent circumferential adhesiveness exceeds 5 micrometers and is 10 micrometers or less

△ (possible): Independent circumferential adhesion value exceeds 10 µm, and 15 µm or less

× (impossible): The value of independent circumferential adhesion exceeds 15 μm

(5) evaluation of sagging of resist pattern

It exposed and developed as mentioned above using the chrome glass photomask as a mask film at the time of exposure. The shape of the 10 micrometer line of the obtained hardening pattern was divided into the following grades.

◎ (excellent): The foot part of a hardening resist is good, and there is no sagging.

○ (good): The break of the foot part of a hardening resist is favorable, and a drooping is very small.

△ (possible): The sagging of 3 micrometers or less is confirmed in the foot part of a hardening resist.

X (impossible): The sagging of more than 3 micrometers is confirmed by the foot part of a hardening resist.

(6) rattling evaluation of sidewall of resist pattern

The laminated body laminated on the board | substrate was exposed and developed as mentioned above using the chrome glass photo mask. The sidewall shape of the resist pattern of the 10 micrometer line of the obtained hardening pattern was divided into the following grades.

○ (good): There is almost no rattling in the formed resist sidewall.

△ (possible): There is very little rattling in the formed resist sidewalls.

× (impossible): There is rattling in several places of the formed resist sidewalls.

(7) Surface condition evaluation of resist pattern

The laminated body laminated on the board | substrate was exposed and developed as mentioned above using the chrome glass photo mask. The resist surface state of the 10 micrometer line of the obtained hardening pattern was ranked and separated by the following.

○ (good): There is almost no depression in the formed resist surface.

△ (possible): There is a slight depression in the formed resist surface.

X (impossible): A depression exists in several places on the formed resist surface.

3. Evaluation result

The evaluation result of an Example and a comparative example is shown to Table 1-1 and Table 1-2. The mass part of P-1-P-2 in Table 1-1 and Table 1-2 is the quantity containing methyl ethyl ketone. In Table 1-1 and Table 1-2, the comparative example 1 does not have an intermediate | middle layer, the comparative example 2 has a thick film thickness of an intermediate | middle layer, and the comparative example 3 has the compound represented by said general formula (I) in an intermediate | middle layer missing. .

Table 1-1

TABLE 1-2

Q-1: Polyvinyl alcohol (PVA-205 by Kuraray Co., Ltd.)

Q-2: polyethylene glycol (weight average molecular weight 400)

Q-3: Polyoxyethylene monomethyl ether (Uniox M-550 by Nippon Oil Holding Co., Ltd., weight average molecular weight 550)

Q-4: polyvinylpyrrolidone (weight average molecular weight 40,000)

P-1: Methyl ethyl ketone solution of the binary copolymer of 80 mass% benzyl methacrylate and 20 mass% methacrylic acid (50 mass% of solid content concentration, the weight average molecular weight 25,000, the acid equivalent 430, dispersion degree 2.7)

P-2: Methyl ethyl ketone solution of the ternary copolymer of 50 mass% of methyl methacrylate, 25 mass% of methacrylic acid, and 25 mass% of styrene (solid content concentration 35 mass%, weight average molecular weight 50,000, acid equivalent 430, dispersion | distribution) 3.1)

M-1: Dimethacrylate of polyalkylene glycol in which an average of 3 moles of ethylene oxide was added to both ends of the polypropylene glycol to which an average of 12 moles of propylene oxide was added.

M-2: Dimethacrylate of polyalkylene glycol which added an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide to both ends of bisphenol A, respectively.

M-3: Dimethacrylate of polyethyleneglycol which added an average of 2 mol of ethylene oxide to both ends of bisphenol A (NK ester 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 (NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.)

M-5: 2,2-bis {4- (methacryloxypentaethoxy) cyclohexyl} propane

M-6: urethane polypropylene glycol dimethacrylate which is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (manufactured by Nippon Oils & Fats, Inc., Brenmer PP1000).

M-7: trimethylolpropane trimethacrylate

M-8: trioxyethyl trimethylol propane triacrylate (NK ester A-TMPT-3EO manufactured by Shin-Nakamura Chemical Industry 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 (Hoistaya Chemical Co., Ltd. Eisen (registered trademark) DIAMOND GREEN GH)

J-2: Loikaw Crystal Violet

L-1: 1 of 1- (2-di-n-butylaminomethyl) -5-carboxybenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxybenzotriazole: 1 mixture

L-2: 3,5-di-t-butyl-4-hydroxyphenyl propionic acid tetraester of pentaerythritol (IRGMOX245 by Chiba Specialty Chemical Co., Ltd.)

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

Claims (7)

A photosensitive resin laminate comprising a support film and an intermediate layer having a layer thickness of 0.1 μm or more and 10 μm or less on the support film and a photosensitive resin layer in this order, wherein the intermediate layer is polyvinyl alcohol and the following general formula (I). Photosensitive resin laminated body containing 1 or more types of compounds chosen from the group which consists of a compound to show R ₁ -O- (CH ₂ CH ₂ O) n ₁ -R ₂ (I) (R ₁ and R ₂ are H or CH ₃ , these may be the same or different, n ₁ is an integer of 3 to 25) WHEREIN: Resin for binders whose photosensitive resin layer is (a) carboxyl group content is 100-600 in acid equivalent, and a weight average molecular weight is 5000-500000: 20-90 mass%, (b) At least 1 type of photopolymerizable unsaturated Compound: 3-70 mass%, (c) Photoinitiator: It is a layer which consists of photosensitive resin composition containing 0.1-20 mass%, The said photosensitive resin laminated body characterized by the above-mentioned. The method of claim 1, The photosensitive resin laminated body formed by laminating | stacking a protective layer further on the said photosensitive resin layer. delete The method according to claim 1 or 2, The photosensitive resin laminated body in which the said resin for binders (a) contains benzyl (meth) acrylate as a copolymerization component. The method according to claim 1 or 2, The photosensitive resin laminated body whose said (b) at least 1 sort (s) of photopolymerizable unsaturated compound is at least 1 sort (s) of photopolymerizable unsaturated compound chosen from the group which consists of a compound represented by following General formula (II)-(VI). [Formula 1]

(Wherein, R ₄ and R ₅ are H or CH ₃ , which may be the same or different, and n ₂ , n ₃ and n ₄ are each independently an integer of 3 to 20) [Formula 2]

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

(Wherein, R ₈ and R ₉ is H or CH _3, which will 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 ~ 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 an integer of 0 to 40. The arrangement of the repeating units of-(DO)-and-(EO)-may be random or block. In the case of a block, the order of-(DO)-and-(EO)-may be one of the cyclohexyl group side) [Formula 4]

(Wherein, R ₁₀ is a divalent organic group, R ₁₁ and R ₁₂ having a carbon number of 4 to 12 is H or CH _3, which are the same or the different. M ₅ and m ₆ is from 1 to 15 are each independently Is an integer) [Chemical Formula 5]

(Wherein 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 ), m ₇ is 1-12, m ₈ Is 0-12 and m ₉ is an integer of 0 to 3. The array of repeating units of-(A'-O)-and-(B'-O)-may be random or a block. The order of A'-O)-and-(B'-O)-may be the phenyl group side) The lamination process of laminating the photosensitive resin laminated body of Claim 1 or 2 to the surface of a metal plate or a metal clad insulation board, the exposure process which peels and exposes a support film, and the image development process which removes an unexposed part by image development, and order. The resist pattern formation method characterized by including as it is. The method according to claim 6, wherein the substrate on which the resist pattern is formed is etched or plated.

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