JP2003307845A - Photosensitive film for forming circuit and method for manufacturing printed-wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive film for forming circuits, which is reduced in its manufacturing cost and is improved in its resolution and pattern accuracy and the yield of printed-wiring boards and a method for manufacturing printed- wiring boards. <P>SOLUTION: The photosensitive film is provided with a supporting film 2, and a cushion layer 3, a non-tacky adhesive resin layer 4 below a layer thickness 10 μm and a tacky adhesive photosensitive resin layer 5 successively laminated and formed on the supporting film 2, in which the interlayer adhesive strength between the cushion layer 3 and the resin layer 4 is lower than the interlayer adhesive strength between the supporting film 2 and the cushion layer 3 and the interlayer adhesive strength between the resin layer 4 and the resin layer 5. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive film for forming a circuit and a method for manufacturing a printed wiring board using the photosensitive film for forming a circuit.

[0002]

2. Description of the Related Art A photosensitive film for forming a circuit, which is used for forming a resist film for plating or etching when manufacturing a printed wiring board, is obtained by applying an adhesive photosensitive resin composition onto a supporting film and drying it. Then, a photosensitive resin layer is formed, and a protective film is further laminated on the photosensitive resin layer. The support film and the adhesive photosensitive resin layer were to be laminated on the substrate of the printed wiring board to be laminated.

A method for manufacturing a printed wiring board using a conventional photosensitive film for forming a circuit will be described below. First, when laminating the photosensitive film for circuit formation on the substrate, after peeling off the protective film of the photosensitive film for circuit formation, place the transfer layer on the substrate with the adhesive photosensitive resin layer facing the substrate side. After that, the transition layer is pressed from the supporting film side with a heating roll to be pressure-bonded. After lamination, a negative mask is placed on the support film, and a light ray for exposure is irradiated through the negative mask to expose the adhesive photosensitive resin layer. After exposure, the negative mask is removed, the support film is peeled off, and then development is performed to obtain an adhesive photosensitive resin layer having the same pattern as the negative mask. The adhesive photosensitive resin layer left on the substrate is used as a resist film to perform a plating or etching process to obtain a printed wiring board.

The supporting film of the photosensitive film for forming a circuit has, for example, a 5% elongation load per unit width at 80 ° C. (value in the longitudinal direction of the film) of 100.
A film of g / mm or more (for example, a film of polyethylene terephthalate (PET)) is used, and the layer thickness of the support film is usually about 20 μm.

The support film requires a certain layer thickness in order to increase the tensile strength of the circuit-forming photosensitive film, and the support film itself must also have a certain degree of hardness.

The adhesive photosensitive resin layer is formed of a photosensitive resin composition whose physical properties at the irradiation site change when it is irradiated with ultraviolet rays or the like, and a suitable resin composition is selected according to the purpose of use. The layer thickness of the adhesive photosensitive resin layer, depending on the purpose,
For example, 25 μm, 33 μm, 40 μm or 50 μm
Is formed.

As the protective film, a film made of polyethylene or the like is used, and the layer thickness thereof is, for example, 30 μm.

As described above, the support film of the photosensitive film for forming a circuit and the adhesive photosensitive resin layer serve as a transfer layer. The transfer layer follows the irregularities of the substrate when laminating. It is also desirable to improve the manufacturing yield by eliminating the unbonded portion between the adhesive photosensitive resin layer and the substrate.

Further, in recent years, the wiring density of printed wiring boards has been increasing, and high resolution is required. In order to increase the resolution of the photosensitive film for forming a circuit, it is effective to reduce the thickness of the adhesive photosensitive resin layer, but since the amount of the adhesive photosensitive resin layer that follows the surface irregularities of the substrate decreases, The conventional photosensitive film for forming a circuit has a problem that the unbonded portion between the substrate and the transfer layer increases and a sufficient manufacturing yield cannot be obtained. Further, in the conventional photosensitive film for circuit formation, as described above, the support film for improving the layer thickness of the support film and the hardness of the support film itself is improved. As a result, the flexibility of the transition layer as a whole becomes insufficient, and it is difficult for the transition layer to follow the irregularities on the surface of the substrate to be laminated.
There has been a problem that the unbonded portion between the substrate and the transition layer is increased and a sufficient manufacturing yield cannot be obtained.

Various techniques have been proposed to reduce the unbonded portion between the substrate and the transition layer. For example, JP-A-57-2
1890 and JP-A-57-2189,
A method is disclosed in which a circuit-forming photosensitive film is laminated after water is applied to a substrate.

[0011]

However, in the above-mentioned method, since it is necessary to uniformly deposit a thin layer of water on the substrate, it is necessary to clean the substrate surface, which is troublesome in the manufacturing process. Was there. Further, when small-diameter through holes and the like are present, the water accumulated in the through holes and the photosensitive resin layer are likely to react with each other, and as a result, developability is lowered and high resolution cannot be obtained. Had a problem.

Further, JP-A-52-154363 discloses a method of laminating a liquid resin on a substrate to form an adhesive intermediate layer and then laminating a photosensitive film for forming a circuit. This method has drawbacks such that the developability and the peeling property of the small-diameter through hole are deteriorated, and the cost is increased by applying the liquid resin.

Further, JP-B-53-31670 and JP-A-51-63702 disclose methods for laminating a circuit-forming film on a substrate under reduced pressure using a vacuum laminator. However, since the apparatus is expensive in this method and it takes time to evacuate, it is rarely used for ordinary circuit formation and is merely used as a laminate for a permanent mask used after conductor formation. Also, when laminating a permanent mask using the vacuum laminator of the present method, it has been desired to reduce unbonded portions and further improve the followability to the conductor.

On the other hand, the conventional circuit-forming film has a problem that the pattern mask is brought into close contact with the supporting film for exposure, so that light scattering occurs on the supporting film and the resolution is deteriorated.

Various techniques have been proposed in order to prevent a decrease in resolution due to light scattering of the support film. For example, JP-A-2000-221688 and JP-A-200
Japanese Patent Laid-Open No. 1-117237 discloses a method of using a polyester film having a haze (measured in accordance with JIS K7105) of 1.0% or less as a support film. According to this method, since the supporting film contains fine particles, and because there is a gap between the adhesive photosensitive resin layer and the pattern mask, resolution can be expected to some extent, but there is room for further improvement. It was

The present invention has been made to solve the above-mentioned problems, and suppresses the manufacturing cost, and also improves the resolution, the pattern accuracy, and the manufacturing yield of printed wiring boards. It is an object to provide a method for manufacturing a wiring board.

[0017]

As a result of various studies aimed at achieving the above-mentioned object, a conventional photosensitive film for forming a circuit comprising three layers of a supporting film, an adhesive photosensitive resin layer and a protective film has been improved, By interposing a cushion layer and a non-adhesive resin layer having a layer thickness of less than 10 μm between the support film and the adhesive photosensitive resin layer, the production cost can be suppressed, and the resolution, pattern accuracy and the production yield of the printed wiring board can be reduced. It is an improvement. More specifically, when laminating a photosensitive film for forming a circuit on a substrate, pressure-bonding is performed from the support film side using a heating roll or the like, but between the support film and the adhesive photosensitive resin layer. When the cushion layer is formed, the cushion layer is freely deformed due to pressurization of a heating roll or the like, so that even when there is unevenness on the substrate, the cushion layer deforms the photosensitive film for circuit formation on the substrate. It is possible to securely adhere to the substrate, and as a result, the non-adhered portion is eliminated to improve the followability to the substrate. In addition to forming the cushion layer, by interposing a non-adhesive resin layer between the cushion layer and the adhesive photosensitive resin layer, the support film and the cushion layer can be separated and exposed. Therefore, it is possible to prevent the resolution from being lowered due to the presence of the supporting film. Further, by making the interlayer adhesive force between the cushion layer and the non-adhesive resin layer lower than the other interlayer adhesive force, when peeling the support film and the cushion layer, it is easy to do without damaging other layers. It can be peeled off.

That is, the photosensitive film for circuit formation of the present invention comprises a support film, a cushion layer formed by sequentially laminating the support film, a non-adhesive resin layer having a layer thickness of less than 10 μm, and an adhesive layer. Adhesive photosensitive resin layer, the interlayer adhesive force between the cushion layer and the non-adhesive resin layer, the interlayer adhesive force between the support film and the cushion layer and the non-adhesive resin layer and the adhesive photosensitive resin It is characterized in that it is lower than the interlayer adhesive strength with the layer.

According to the present invention, when laminating on the substrate to be laminated, without increasing the production cost,
In addition, transfer can be performed without causing a transfer failure due to minute dust, bubbles, unevenness of the substrate surface, and the like.
The support film and the cushion layer can be easily peeled off, the resolution and the accuracy of the resist pattern can be improved, and the production yield of the printed wiring board can be greatly improved, which is useful for increasing the density and resolution of the printed wiring.

In the above invention, the layer thickness is 10 μm.
A protective film is formed on the adhesive photosensitive resin layer on the side facing the non-adhesive resin layer of less than m, and the interlayer adhesive force between the adhesive photosensitive resin layer and the protective film is the cushion. It is preferably lower than the interlayer adhesive force between the layer and the non-adhesive resin layer having a layer thickness of less than 10 μm.

According to the present invention, the handling property is improved by forming the protective film.

In the above invention, the adhesive photosensitive resin layer comprises (a) a binder polymer and (b) 2,2-
Bis (4-((meth) acryloxypolyalkoxy) phenyl) propane, and (c) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond,
(D) It is desirable to use an adhesive photosensitive resin material containing at least a photopolymerization initiator.

According to the present invention, an adhesive photosensitive resin layer having excellent photosensitivity, adhesion, resolution, chemical resistance, plating resistance, etching resistance, laminating property, developability, mechanical strength and flexibility is obtained. be able to.

Further, in the above invention, the cushion layer is preferably made of a material whose main component is a copolymer containing ethylene as an essential copolymerization component. Specifically, the copolymer is a copolymer of ethylene. EVA (ethylene-vinyl acetate copolymer) having a polymerization ratio of 60 to 90 mass% or EEA (ethylene-ethyl acrylate copolymer) having a copolymerization ratio of ethylene of 60 to 90 mass% is preferable. The layer thickness of the cushion layer is 1 μm to 100 μm.
It is desirable that the range is up to μm.

According to the present invention, it is possible to obtain a film for forming a circuit in which the transition layer can favorably follow the irregularities on the surface of the substrate without increasing the production cost and can greatly improve the manufacturing yield of the printed wiring board. You can

In the above invention, the (a) binder polymer contained in the adhesive photosensitive resin material forming the adhesive photosensitive resin layer contains methacrylic acid as an essential copolymerization component, and (a) the binder polymer. Has an acid value of 1
0 to 500 mg KOH / g, and (a) the binder polymer has a weight average molecular weight of 20,000 to 300,000.
It is preferably 0.

According to the present invention, it is possible to obtain a circuit-forming photosensitive film having excellent alkali developability.

Further, in the above invention, the binder polymer (a) contains styrene or a styrene derivative as an essential copolymerization component, and contains styrene or a styrene derivative in an amount of 0.1 to 40% by mass based on all the copolymerization components. It is desirable to do.

According to the present invention, a photosensitive film for circuit formation having excellent chemical resistance can be obtained.

Further, in the above invention, 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane contained in the adhesive photosensitive resin material is represented by the general formula (I).

[Chemical 2] (In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, X ¹ and X ² each independently represent an alkylene group having 2 to 6 carbon atoms, and p and q are p + q = 4 to 40. Is a positive integer selected so that X ¹ and X ² are preferably ethylene groups.

According to the present invention, it is possible to obtain a photosensitive film for circuit formation which is excellent in photosensitivity and chemical resistance (plating resistance).

In the method for manufacturing a printed wiring board according to the present invention, the above-mentioned photosensitive film for circuit formation is laminated on the substrate so that the adhesive photosensitive resin layer is in contact with the substrate, and then laminated. It is characterized in that the support film and the cushion layer of the photosensitive film for forming a circuit are peeled off, then exposed through a pattern mask and then developed.

When the protective film is formed on the surface of the circuit-forming photosensitive film, the protective film is peeled off, and then the adhesive photosensitive resin layer of the circuit-forming photosensitive film is placed on the substrate. It is preferable that the substrates are laminated so as to be in contact with the substrate, the support film and the cushion layer are peeled off, and then exposed through a pattern mask and developed.

According to the present invention, the transfer layer favorably follows the irregularities of the surface of the substrate to be laminated without increasing the production cost, and the exposure is performed after peeling the support film and the cushion layer. It is possible to further improve the resolution and the accuracy of the resist pattern, and to greatly improve the manufacturing yield of the printed wiring board.

Further, in the above invention, it is desirable that the pattern mask is adhered onto the non-adhesive resin layer having a layer thickness of less than 10 μm after the support film and the cushion layer of the photosensitive film for circuit formation are peeled off. .

According to the present invention, the pattern mask after exposure can be easily peeled from the non-adhesive resin layer having a layer thickness of less than 10 μm without contamination.

Further, according to the present invention, even when the substrates are stacked and stored after the exposure, the photosensitive resin layer is formed from the non-adhesive resin layer having a layer thickness of less than 10 μm, so that the photosensitive resin layer can be formed on the substrate or another substrate. Does not transfer to a non-adhesive resin layer having a layer thickness of less than 10 μm,
It is possible to ensure excellent handleability.

[0038]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing a photosensitive film for circuit formation and a printed wiring board according to the present invention will be described in detail below. In addition, (meth) acrylic acid described below means acrylic acid and methacrylic acid corresponding thereto,
(Meth) acrylate means acrylate and corresponding methacrylate, and (meth) acryloyl group means acryloyl group and corresponding methacryloyl group.

First, each layer constituting the photosensitive film for forming a circuit will be described. FIG. 1 is an enlarged view showing a cross section of a circuit-forming photosensitive film 1. As shown in this figure, a cushion layer 3 and a non-adhesive resin having a layer thickness of less than 10 μm are provided on a support film 2. The layer 4, the adhesive photosensitive resin layer 5, and the protective film 6 are sequentially laminated and configured.

[Support Film] The support film is not particularly limited, but the layer thickness of the support film is preferably 2 to 100 μm, more preferably 5 to 20 μm, and particularly preferably 8 to 16 μm. . This is because if the layer thickness of the support film is less than 2 μm, the support film tends to break when peeled off, and if it exceeds 100 μm, the conformability to the irregularities on the surface of the object to be laminated tends to decrease.

Examples of the supporting film include polyester or polypropylene such as polyethylene terephthalate, and polymer films such as polypropylene and polyethylene having heat resistance and solvent resistance. Examples of the available support film include Teijin DuPont Films Co., Ltd., product name G2-16 and the like.

[Cushion Layer] The cushion layer is a copolymer whose main component is ethylene as an essential copolymerization component.
VA (ethylene-vinyl acetate copolymer) or EEA
(Ethylene-ethyl acrylate copolymer) is used.
The ethylene or EVA copolymerization ratio used at this time is 60 to 90% by mass, preferably 60 to 80% by mass, and more preferably 65 to 80% by mass. When the ethylene copolymerization ratio is less than 60% by mass, the adhesion of the cushion layer is high, and the layer thickness laminated on the cushion layer is 10 μm.
This is because the adhesiveness to the non-adhesive resin layer below is too high, and it becomes difficult to separate the cushion layer and the non-adhesive resin layer. On the contrary, when the ethylene copolymerization ratio exceeds 90% by mass, the adhesiveness between the cushion layer and the photosensitive resin layer is deteriorated and it becomes difficult to prepare a film including the cushion layer.

The layer thickness of the cushion layer is 1 to 100 μm, preferably 10 to 50 μm, more preferably 1
It is 5 to 40 μm. When the layer thickness is 1 μm or less, the ability to follow the irregularities on the surface of the object to be laminated tends to deteriorate. On the other hand, when the layer thickness exceeds 100 μm, the cost tends to increase.

[Non-adhesive resin layer having a layer thickness of less than 10 μm] The components of the non-adhesive resin layer having a layer thickness of less than 10 μm are not particularly limited, but are preferably alkali-soluble components. When the alkali-insoluble component is used, a step of removing the non-adhesive resin layer having a layer thickness of less than 10 μm is required when the adhesive photosensitive resin layer is alkali-developed after exposure, which tends to increase the production process and increase the cost. Because there is.

The thickness of the non-adhesive resin layer having a layer thickness of less than 10 μm is not particularly limited as long as it is less than 10 μm, but is preferably 1 to 6 μm, more preferably less than 2 μm. When the layer thickness is 10 μm or more, when the adhesive photosensitive resin layer is exposed to light, light scattering occurs in the non-adhesive resin layer, and resolution and adhesion tend to be deteriorated.

The adhesive force of the non-adhesive resin layer having a layer thickness of less than 10 μm to the mask pattern or the substrate should be such that transfer of the non-adhesive resin layer does not occur at 180 ° C. peel strength (23 ° C., 60% RH). There is no particular limitation, but 5N / m
Less than 3 N / m, preferably less than 1 N / m. If the adhesive strength is 5 N / m or more, the non-adhesive resin layer may have a problem such as transfer to a mask pattern or the like, and the manufacturing yield of the printed wiring board tends to be deteriorated.

[Adhesive Photosensitive Resin Layer] The thickness of the adhesive photosensitive resin layer is not particularly limited, but from the viewpoint of increasing the density of the printed wiring, it is 0.1 to 40 μm, preferably 3 to 20 μm.
m, more preferably 6 to 15 μm. This is because when the layer thickness of the adhesive photosensitive resin layer is 40 μm or more, resolution and adhesiveness tend to deteriorate.

The interlayer adhesion between the cushion layer and the non-adhesive resin layer having a layer thickness of less than 10 μm is 180 ° C. peel strength (23
At 60 ° C. and 60% RH), there is no particular limitation as long as it is smaller than the interlayer adhesive force between the support film and the cushion layer and the interlayer adhesive force between the non-adhesive resin layer having a layer thickness of less than 10 μm and the adhesive photosensitive resin layer. From the viewpoint of productivity, the interlayer adhesive force between the cushion layer and the non-adhesive resin layer having a layer thickness of less than 10 μm is 1 to 100 N / m, preferably 2 to 30 N / m, and more preferably 4 to 10 N. / M. This is because when the interlayer adhesive strength is 100 N / m or more, the adhesive photosensitive resin layer tends to partly peel off from the substrate when the support film and the cushion layer are peeled off.

[Protective Film] Since the protective film is peeled off before being laminated, it has flexibility, can adhere to the adhesive photosensitive resin layer, and is not damaged by the temperature of the drying oven. , But not particularly limited, for example, paper, release paper, polyester such as polyethylene terephthalate, polymethylpentene, polypropylene, polyolefin such as polyethylene, polyvinyl fluoride, halogen-containing vinyl polymer such as polyvinyl chloride, polyamide such as nylon, Examples include cellulose such as cellophane, and films such as polystyrene. In addition, these protective films may be transparent or non-transparent, and may be subjected to a release treatment.

Available protective films include Oji Paper Co., Ltd., product name E-200H, Tama Poly Co., Ltd.,
Product name NF-13 etc. are mentioned.

The layer thickness of the protective film is not particularly limited, but in consideration of the size when wound in a roll shape, it is 5 to 5.
The thickness is preferably 200 μm, more preferably 10 to 100 μm, and particularly preferably 10 to 50 μm.

Further, in order to easily form the transfer layer by peeling off the protective film, the interlayer adhesive force between the protective film and the tacky photosensitive resin layer is preferably lower than the other interlayer adhesive forces. .

The circuit-forming photosensitive film formed by laminating each of the above layers can be wound into a roll and stored. The photosensitive film for circuit formation includes the above-mentioned support film, cushion layer, and layer thickness 10
In addition to a non-adhesive resin layer having a thickness of less than μm, an adhesive photosensitive resin layer, and a protective film used as necessary, it may have an intermediate layer or a protective layer such as an adhesive layer, a light absorbing layer, a gas barrier layer. .

The adhesive photosensitive resin material forming the adhesive photosensitive resin layer includes (a) a binder polymer and (b) 2,2-bis (4-((meth) acryloxypolyalkoxy). ) Phenyl) propane, (c) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond, and (d) a photopolymerization initiator are contained at least. The components of each material up to d) will be described.

First, (b) 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane will be described. The 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane is not particularly limited, but for example, a compound represented by the general formula (I) is preferable. The general formula (I)
In the above, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and preferably a methyl group. In the general formula (I), X ¹ and X ² each independently represent an alkylene group having 2 to 6 carbon atoms, preferably an ethylene group or a propylene group, and particularly preferably an ethylene group. In the general formula (I), p and q are p + q = 4 to 40
Is a positive integer selected so that it is preferably 6 to 34, more preferably 8 to 30,
Particularly preferred is 8 to 28, very preferred is 8 to 20, very particularly preferred is 8 to 16, and most preferred is 8 to 12. p +
When q is less than 4, the compatibility with the (a) binder polymer decreases, and when the photosensitive film for circuit formation is laminated on the substrate, it tends to peel off, and p + q is 4
This is because if it exceeds 0, the hydrophilicity increases, the resist image tends to peel off during development, and the plating resistance to solder plating or the like tends to decrease.

Examples of the alkylene group having 2 to 6 carbon atoms include an ethylene group, a propylene group, an isopropylene group, a butylene group, a pentylene group and a hexylene group. From the viewpoint of resolution and plating resistance, the ethylene group is preferable. Alternatively, it is preferably an isopropylene group.

The aromatic ring in the general formula (I) may have a substituent, and examples of the substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms, and 3 to 1 carbon atoms.
A cycloalkyl group having 0, an aryl group having 6 to 18 carbon atoms,
Phenacyl group, amino group, alkylamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, carbon number 1
-10 alkyl mercapto group, aryl group, hydroxyl group,
Hydroxyalkyl group having 1 to 20 carbon atoms, carboxyl group, carboxyalkyl group having 1 to 10 carbon atoms in alkyl group, acyl group having 1 to 10 carbon atoms in alkyl group, alkoxy group having 1 to 20 carbon atoms, carbon An alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group having 2 to 10 carbon atoms or a group containing a heterocycle, and a substituent thereof And an aryl group substituted with. The above-mentioned substituents may form a condensed ring. Further, the hydrogen atom in these substituents may be substituted with the above-mentioned substituent such as a halogen atom. When the number of substituents is 2 or more, the 2 or more substituents may be the same or different.

Examples of the compound represented by the above general formula (I) include 2,3-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-(( (Meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) ) Phenyl) propane and other bisphenol A (meth) acrylate compounds.

Examples of 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4
-((Meth) acryloxyheptaethoxy) phenyl)
Propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonaethoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acry) Roxydodecaethoxy) phenyl) propane, 2,2-
Bis (4-((meth) acryloxytridecaethoxy)
Phenyl) propane, 2,2-bis (4-((meth) acryloxytetradecaethoxy) phenyl) propane,
2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxyhexadecaethoxy) phenyl) propane and the like, and 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is B
PE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) is commercially available, and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is BPE-1300 (new It is commercially available as Nakamura Chemical Co., Ltd., product name) and is used alone or in combination of two or more kinds.

Examples of the 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane, 2,2-bis (4
-((Meth) acryloxytripropoxy) phenyl)
Propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentapropoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2
-Bis (4-((meth) acryloxyheptapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth ) Acryloxynonapropoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydodeca) Propoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl) propane, 2,
2-bis (4-((meth) acryloxytetradecapropoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxypentadecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexadecapropoxy) phenyl) propane, and the like, which may be used alone or in combination of two or more. It

Examples of 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include, for example, 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy)). Phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane,
2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane and the like can be mentioned, and they are used alone or in combination of two or more kinds.

Next, the binder polymer (a) will be described. The weight average molecular weight of the binder polymer is 2
It is preferably 30,000 to 300,000 and 4
It is more preferably from 0000 to 150,000.
If the weight average molecular weight is less than 20,000, the developer resistance tends to decrease, and conversely, the weight average molecular weight of 300,
If it exceeds 000, the developing time tends to be long. In addition, the mass average molecular weight and the number average molecular weight are measured by gel permeation chromatography, and the values converted into standard polystyrene are used. Also,
The binder polymer has a mass average molecular weight of 20,000-
There is no particular problem as long as it is 300,000, and examples thereof include acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin, etc., which may be used alone or in combination of two or more. Can be used in combination. From the viewpoint of alkali developability, acrylic resin is preferable.

The (a) binder polymer can be produced, for example, by radically polymerizing a polymerizable monomer. As the polymerizable monomer, for example, styrene, vinyltoluene, α-methylstyrene and other α-
Polymerizable styrene derivative substituted at position or aromatic ring, acrylamide such as diacetone acrylamide, acrylonitrile, vinyl alcohol esters such as vinyl-n-butyl ether, (meth) acrylic acid alkyl ester, (meth) acrylic Acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2 , 3,4-Tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl ( (Meth) acrylic acid, Murray Acid, maleic anhydride, monomethyl maleate, monoethyl maleate, maleic acid monoester such as monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like. To be As the above-mentioned (meth) acrylic acid alkyl ester, for example, general formula (II)

Embedded image CH ₂ ═C (R ³ ) —COOR ⁴ (II) (in the formula, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group having 1 to 12 carbon atoms). And compounds in which an alkyl group of these compounds is substituted with a hydroxyl group, an epoxy group, a halogen group or the like.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ⁴ in the general formula (II) include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group,
Examples thereof include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and structural isomers thereof. Examples of the monomer represented by the general formula (II) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (Meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid 2-ethylhexyl ester,
(Meth) acrylic acid nonyl ester, (meth) acrylic acid decyl ester, (meth) acrylic acid undecyl ester, (meth) acrylic acid dodecyl ester and the like can be mentioned, and they can be used alone or in combination of two or more kinds. it can.

Further, the binder polymer (a) preferably contains a carboxyl group from the viewpoint of alkali developability. For example, a polymerizable monomer having a carboxyl group and another polymerizable monomer are radically polymerized. It can be manufactured.

Further, the binder polymer (a) preferably contains styrene or a styrene derivative as a polymerizable monomer from the viewpoint of flexibility. As the styrene derivative, for example, a polymerizable styrene derivative such as vinyltoluene, α-methylstyrene, p-methylstyrene, or p-ethylstyrene can be used.

In order to improve both the adhesiveness and the peeling property by using styrene or a styrene derivative as a copolymerization component, styrene or a styrene derivative is added to the copolymerization component in an amount of 0.1.
To 40% by mass, more preferably 1 to 40% by mass.
It is preferably 28% by mass, particularly preferably 1.5 to 27% by mass. If the content of the copolymerization component of styrene or a styrene derivative is less than 0.1% by mass, the adhesion tends to be poor, and if it exceeds 40% by mass, the peeled pieces tend to be large and the peeling time tends to be long. The (a) binder polymer can be used alone or in combination of two or more kinds. Examples of the binder polymer in the case of using two or more kinds in combination include two or more kinds of binder polymers composed of different copolymerization components, two or more kinds of binder polymers having different weight average molecular weights, and two or more kinds of different dispersities. Examples include binder polymers.

The acid value of the binder polymer (a) is preferably 100 to 500 mgKOH / g, more preferably 100 to 300 mgKOH / g. This is because when the acid value is less than 100 mgKOH / g, the developing time tends to be delayed, and when it exceeds 500 mgKOH / g, the resistance of the photocured resist to the developing solution tends to decrease.

Further, (c) the photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond will be described. Examples of the photopolymerizable compound include a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane. A compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid, a urethane monomer, nonylphenyldioxylene (meth) acrylate, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyl Oxyethyl-o-phthalate, β-hydroxyethyl-β′-
(Meth) acryloyloxyethyl-o-phthalate,
Examples thereof include β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate and (meth) acrylic acid alkyl ester.

Examples of the compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid include polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and propylene group. Number 2
To polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate , Trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropane tetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate Acrylate, polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate.

Examples of the α, β-unsaturated carboxylic acid include (meth) acrylic acid.

Examples of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxydecaethoxy) phenyl) and the like, and 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is BEP-500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). ) Is commercially available.

Examples of the glycidyl group-containing compound include trimethylolpropane triglycidyl ether tri (meth) acrylate and 2,2-bis (4-
(Meth) acryloxy-2-hydroxy-propyloxy) phenyl and the like.

As the urethane monomer, for example, a (meth) acrylic monomer having an OH group at the β-position and isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate,
Addition reaction product with 1,6-hexamethylene diisocyanate, tris ((meth) acryloxytetraethylene glycol isocyanate) hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, E
Examples thereof include O- and PO-modified urethane di (meth) acrylate. EO represents ethylene oxide, and EO
The modified compound has a block structure of an ethylene oxide group. Further, PO represents propylene oxide, and the PO-modified compound has a block structure of propylene oxide group.

Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, and (meth)
Acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester and the like are mentioned, and they are used alone or in combination of two or more kinds.

Finally, the photopolymerization initiator (d) will be described. Examples of the photopolymerization initiator include benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michlerketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-
4'-Dimethylaminobenzophenone, 2-benzyl-
2-dimethylamino-1- (4-morpholinophenyl)
-Aromatic ketones such as butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone,
Octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone,
Quinones such as 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl 1,4-naphthoquinone and 2,3-dimethylanthraquinone, benzoin methyl ether, benzoin ethyl Benzoin ether compounds such as ether and benzoin phenyl ether, benzoin compounds such as benzoin, methylbenzoin and ethylbenzoin, benzyl derivatives such as benzyldimethylketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2 -(O-chlorophenyl)-
4,5-di (methoxyphenyl) imidazole dimer,
2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,
2,4,5-triarylimidazole dimer such as 5-diphenylimidazole dimer and 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 9
Examples include acridine derivatives such as -phenylacridine, 1,7-bis (9,9'-acridinyl) heptane, N-phenylglycine, N-phenylglycine derivatives, and coumarin compounds. Further, the substituents of the aryl groups of the two 2,4,5-triarylimidazoles may be the same and may give a target compound, or may be different and give an asymmetric compound. Also, a thioxanthone compound and a tertiary amine compound may be combined, such as a combination of diethylthioxanthone and dimethylaminobenzoic acid. Also, from the viewpoint of adhesion and sensitivity, 2, 4, 5
-Triarylimidazole dimers are more preferable, and they are used alone or in combination of two or more kinds.

Further, the compounding amounts of the materials contained in the adhesive photosensitive resin material forming the adhesive photosensitive resin layer will be described in detail.

(A) The blending amount of the binder polymer is
(A) Binder polymer, (b) 2,2-bis (4-
40 to 80 parts by mass based on 100 parts by mass of the total amount of ((meth) acryloxypolyalkoxy) phenyl) propane and (c) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond. Is preferred,
It is more preferable that the amount is 45 to 70 parts by mass. If the compounding amount of the (a) binder polymer is less than 40 parts by mass, the photocured product tends to be brittle, and when used as a photosensitive film for circuit formation, the coating property tends to be poor, and exceeds 80 parts by mass. This is because the photosensitivity tends to be insufficient.

Amount of (b) 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane and (c) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond. Has a (a) binder polymer, (b) 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane and (c) at least one polymerizable ethylenically unsaturated bond. The total amount of the photopolymerizable compound is preferably 20 to 60 parts by mass, and 30 to 30 parts by mass.
More preferably, it is 55 parts by mass. This blend amount is 2
If it is less than 0 parts by mass, the photosensitivity tends to be insufficient, and 6
If it exceeds 0 parts by mass, the photocured product tends to become brittle.

The compounding amount of (d) the photopolymerization initiator is (a) the binder polymer, (b) 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane and (c) at least 1. It is preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the total amount of the photopolymerizable compound having one polymerizable ethylenically unsaturated bond, and 0.2.
More preferably, it is from 10 to 10 parts by mass. If the compounding amount of the photopolymerization initiator (d) is less than 0.1 parts by mass, the photosensitivity tends to be insufficient, and if it exceeds 20 parts by mass, the absorption on the surface of the composition increases during exposure. Internal photocuring tends to be inadequate.

In the adhesive photosensitive resin layer, if necessary, a dye such as malachite green, a photo-coloring agent such as tribromophenyl sulfone or leuco crystal violet, a thermal color-preventing agent, p-toluene sulfonamide. Such as plasticizers, pigments, fillers, defoamers, flame retardants, stabilizers, adhesion promoters, leveling agents, peeling accelerators, antioxidants,
(A) a binder polymer, (b) 2,3-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane, and (c) at least one polymerizable ethylene, such as a fragrance, an imaging agent, and a thermal crosslinking agent. Each of them may be contained in an amount of about 0.01 to 20 parts by mass with respect to 100 parts by mass of the total amount of the photopolymerizable compound having a polyunsaturated bond, and may be used alone or in combination of two or more kinds.

The adhesive photosensitive resin layer may be a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or the like, if necessary. It can be applied as a solution having a solid content of 30 to 60 mass% by being dissolved in the mixed solvent of.

Further, the wavelength of the adhesive photosensitive resin layer is 365.
The transmittance with respect to ultraviolet rays of nm is preferably 5 to 75%, more preferably 7 to 60%, and 10
It is particularly preferable that it is -40%. If the transmittance is less than 5%, the adhesion tends to be poor, and if it exceeds 75%, the resolution tends to be poor. The transmittance can be measured by a UV spectrometer, and examples of the UV spectrometer include a 228A type W beam spectrophotometer manufactured by Hitachi, Ltd.

Next, a method of manufacturing the photosensitive film for forming a circuit will be described.

For the photosensitive film for forming a circuit, a solution of the cushion layer material is uniformly applied onto a support film,
It is dried with a hot air convection dryer of 150 ° C., a solution of a non-adhesive resin layer material having a layer thickness of less than 10 μm is uniformly applied on it, and dried with a hot air convection dryer of 30 to 150 ° C. A solution of the adhesive photosensitive resin layer material is evenly applied thereon, and dried by a hot air convection dryer at 30 to 150 ° C. to prepare.

For the photosensitive film for forming a circuit, a cushion layer material solution, a non-adhesive resin layer material solution having a layer thickness of less than 10 μm and an adhesive photosensitive resin layer material solution are uniformly applied on a support film. After that, it may be dried using a hot air convection dryer at 30 to 150 ° C. to prepare a photosensitive film for circuit formation. In addition, the production of the photosensitive film for forming a circuit is not limited to the above-mentioned method, and other methods may be used.

A method for producing a printed wiring board by forming the circuit-forming photosensitive film produced by the above method on a substrate will be described. First, if a protective film is present, after removing the protective film, the layer thickness is 10 μm.
The non-adhesive resin layer and the adhesive photosensitive resin layer of less than below may be laminated by pressure bonding to the circuit-forming substrate while heating, and may be laminated under reduced pressure from the viewpoint of adhesion and followability. preferable. The surface to be laminated is usually a metal surface, but there is no particular limitation. The heating temperature of the non-adhesive resin layer and the adhesive photosensitive resin layer having a layer thickness of less than 10 μm is 70 to
The temperature is preferably 130 ° C, and the pressure is 0.1 to 1.
The pressure is preferably about 0 MPa, but these conditions are not particularly limited. Further, if the non-adhesive resin layer and the adhesive photosensitive resin layer having a layer thickness of less than 10 μm are heated in the range of 70 to 130 ° C., it is not necessary to preheat the circuit-forming substrate in advance, but the stackability is improved. To further improve
It is also possible to preheat the circuit-forming substrate.

Next, after peeling off the support film and the cushion layer, an actinic ray is imagewise irradiated through a negative or positive mask pattern called artwork. As the light source of the actinic ray, a known light source such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, or a xenon lamp that effectively emits ultraviolet rays is used. In addition, a flood light bulb for photography, a solar lamp or the like that effectively radiates visible light is also used.

The exposed circuit-forming boards may be stacked and stored, but when pressure such as the weight of the circuit-forming boards is applied, a non-adhesive resin layer having a layer thickness of less than 10 μm is formed on another circuit-forming board or In order to prevent transfer to another non-adhesive resin layer having a layer thickness of less than 10 μm, Teflon is provided between the circuit forming substrates.
Insert a (registered trademark) sheet, polyethylene sheet, or the like.

Further, the unexposed part is removed by wet development, dry development or the like to develop the resist pattern. In the case of wet development, an alkaline aqueous solution, an aqueous developer, using a developer corresponding to the photosensitive resin composition such as an organic solvent, for example, by a known method such as a spray method, rocking dipping, brushing, scraping, etc. develop.
As the developer, a safe and stable developer having good operability such as an alkaline aqueous solution is used. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium or potassium hydroxides, alkali carbonates such as lithium, sodium, potassium or ammonium carbonates or bicarbonates, potassium phosphate, phosphoric acid. Alkali metal phosphates such as sodium, sodium pyrophosphate, alkali metal pyrophosphates such as potassium pyrophosphate, and the like are used. As the alkaline aqueous solution used for development, a dilute solution of 0.1 to 5 mass% sodium carbonate, a dilute solution of 0.1 to 5 mass% potassium carbonate, a dilute solution of 0.1 to 5 mass% sodium hydroxide, 0.
A dilute solution of 1 to 5 mass% sodium tetraborate or the like is preferable. The pH of the alkaline aqueous solution used for development is 9 to
The range is preferably 11 and the temperature is adjusted according to the developability of the photosensitive resin layer. Further, a surface active agent, a defoaming agent, a small amount of an organic solvent for accelerating development may be mixed in the alkaline aqueous solution. The aqueous developer comprises water or an aqueous alkaline solution and one or more organic solvents. In addition to the above substances, examples of the alkaline substance include borax, sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol, 1,3-diaminopropanol-2, morpholine and the like can be mentioned. The pH of the developer is preferably as small as possible within the range where the resist can be sufficiently developed,
The pH is preferably 8-12, more preferably 9-10.
It is preferable that Examples of the organic solvent include triacetone alcohol, acetone, ethyl acetate, carbon number 1
Alkoxy ethanol having an alkoxy group of 4 to 4, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol, monobutyl ether and the like can be mentioned, alone or 2
Used in combination with more than one type. Usually, the concentration of the organic solvent is preferably 2 to 90% by mass, and the temperature thereof can be adjusted according to the developability. Further, in the aqueous developer, for example, a small amount of an activator, an antifoaming agent or the like can be mixed in the interface. As an organic solvent-based developer used alone, 1,1,1-trichloroethane, N-
Methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ-butyrolactone and the like can be mentioned. It is preferable to add water to these organic solvents in the range of 1 to 20 mass% in order to prevent ignition. If desired, two or more developing methods may be used in combination. Development methods include dip method, battle method, spray method, brushing, slapping method, etc., and the high pressure spray method is most suitable for improving resolution.

As the processing after development, 60 to 60
The resist pattern may be further cured by heating at about 250 ° C. or exposure at about 0.2 to 10 mJ / cm ² .

For the etching of the metal surface performed after the development, cupric chloride solution, ferric chloride solution, alkali etching solution or hydrogen peroxide type etching solution can be used. It is desirable to use a ferric solution.

When a printed wiring board is manufactured using the above-mentioned photosensitive film for circuit formation, the surface of the circuit formation substrate is treated by a known method such as etching using the developed resist pattern as a mask. Examples of the plating method include copper sulfate plating, copper plating such as copper pyrophosphate plating, solder plating such as high-throw solder plating, Watts bath (nickel sulfate-nickel chloride) plating,
Examples thereof include nickel plating such as nickel sulfamate plating, gold plating such as hard gold plating and soft gold plating. Then, the resist pattern can be stripped with a stronger alkaline aqueous solution than the alkaline aqueous solution used for development, for example. As the strongly alkaline aqueous solution, for example, a 1 to 10 mass% sodium hydroxide aqueous solution, a 1 to 10 mass% potassium hydroxide aqueous solution, etc. are used. Examples of the peeling method include a dipping method and a spray method. The dipping method or the spray method may be used alone or in combination. Also, the printed wiring board on which the resist pattern is formed is
It may be a multilayer printed wiring board.

Next, actual examples will be described in more detail with reference to Examples 1 to 4 and Comparative Examples 1 to 8 as examples. The present invention is not limited to the examples below.

[0095]

EXAMPLES First, in producing a photosensitive film for forming a circuit, first, a cushion layer, a non-adhesive resin layer having a layer thickness of less than 10 μm, and an adhesive photosensitive resin layer are formed on a support film. Adjustment of each material was performed.

[Adjustment of Cushion Layer Material] As shown in Table 1, as a material for forming the cushion layer, ethylene was blended in toluene by changing the copolymerization ratio of ethylene to prepare a solution from solution B-I to solution B-III. Each material was adjusted. The solution B-I was used as an example, and the solution B-II and the solution B-III were used as comparative examples.

[0097]

[Table 1] [Adjustment of non-adhesive resin layer material having a layer thickness of less than 10 μm] Table 2
The materials shown in (3) were blended to prepare a solution CI as a material for forming a non-adhesive resin layer having a layer thickness of less than 10 μm.

[0098]

[Table 2] [Adjustment of Adhesive Photosensitive Resin Layer Material] As shown in Table 3,
In a solvent, a binder polymer as the component (a), (b)
2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane as a component, a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond as a component (c), and a component (d) As a photopolymerization initiator, and further, a color former and a dye, respectively,
Solutions D-I and D-II were prepared as adhesive photosensitive resin layer materials. In addition, the solution D-II was used as a material in which the component (b), 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane, was not blended, in Comparative Examples.

[0099]

[Table 3] A circuit-forming film was produced using the adjusted materials for the respective layers.

[Preparation of Film for Forming Circuit (Examples 1 to 1
Example 4 and Comparative Examples 1 to 8)] Example 1 (Circuit forming film <1>) As a supporting film, a polyethylene terephthalate film having a layer thickness of 16 μm (trade name: X92-16, Teijin DuPont Films Ltd.) Manufactured) was used. On the support film, the solution of the cushion layer material BI was dried to a layer thickness of 20 μm.
It was evenly coated so as to have a thickness of m, and dried by a hot air convection dryer at 80 ° C. for 10 minutes. A solution of the non-adhesive resin layer material C-I having a layer thickness of less than 10 μm is further dried thereon to have a layer thickness of 2 μm.
Was uniformly applied and dried in a hot air convection dryer at 100 ° C. for 10 minutes. Further, a solution of the adhesive photosensitive resin layer material D-I was evenly applied thereon so that the layer thickness after drying would be 10 μm, and the solution was dried by a hot air convection dryer at 100 ° C.
Dry for 0 minutes. Then, as a protective film, the layer thickness is 20
μm biaxially oriented polypropylene film (trade name: E-20
A photosensitive film <1> for circuit formation was prepared by protecting with 0H, Oji Paper Co., Ltd.

Example 2 (Preparation of Film <2> for Circuit Formation) In Example 1, the thickness of the adhesive photosensitive resin layer was 20 μm.
A photosensitive film <2> for circuit formation was produced in the same manner as in Example 1 except that m was changed.

Example 3 (Circuit-forming film <3>) A circuit-forming film was formed in the same manner as in Example 1 except that the non-adhesive resin layer having a layer thickness of less than 10 μm had a thickness of 5 μm. A photosensitive film <3> was produced.

Example 4 (Production of Circuit-Forming Film <4>) Example 4 was carried out except that the cushion layer had a layer thickness of 10 μm and the (D) adhesive photosensitive resin layer had a layer thickness of 20 μm. Photosensitive film for circuit formation <4 as in Example 1
> Was made.

Comparative Example 1 (Circuit-forming film <5>) A polyethylene terephthalate film (trade name: X92-16, manufactured by Teijin DuPont Films Ltd.) having a layer thickness of 16 μm was used as a support film, and the support film was formed on the support film. The layer thickness of the cushion layer material BI after drying is 20 μm.
Was uniformly applied and dried in a hot air convection dryer at 80 ° C. for 10 minutes. Then, a solution of the adhesive photosensitive resin layer material D-I was evenly applied onto it so that the layer thickness after drying would be 10 μm, and dried with a hot air convection dryer at 100 ° C.
Dry for minutes. Then, as a protective film, layer thickness 20μ
m biaxially oriented polypropylene film (trade name: E-200
H, manufactured by Oji Paper Co., Ltd., was used to prepare a photosensitive film <5> for circuit formation.

Comparative Example 2 (Circuit-forming film <6>) A polyethylene terephthalate film (trade name: X92-16, manufactured by Teijin DuPont Films Ltd.) having a layer thickness of 16 μm was used as a support film, and the support film was formed on the support film. A solution of the non-adhesive resin layer material CI having a layer thickness of less than 10 μm is evenly applied so that the layer thickness after drying is 2 μm, and the temperature is 100 ° C.
Was dried for 10 minutes by the hot air convection dryer. Then, a solution of the adhesive photosensitive resin layer material D-I was uniformly applied thereon so that the layer thickness after drying would be 10 μm, and dried for 10 minutes by a hot air convection dryer at 100 ° C. Then, as a protective film, a biaxially oriented polypropylene film (trade name: E-200H, manufactured by Oji Paper Co., Ltd.) having a layer thickness of 20 μm was used for protection to prepare a photosensitive film <6> for circuit formation.

Comparative Example 3 (Circuit forming film <7>) A circuit forming photosensitive film <7> was prepared in the same manner as in Example 1 except that the cushion layer material was B-II. Comparative Example 4 (Circuit forming film <8>) In Example 1, an attempt was made to prepare a circuit forming photosensitive film <8> in the same manner as in Example 1 except that the cushion layer material was B-III. Cushion layer material B-II
A uniform solution of I could not be obtained, and a photosensitive film <8> for circuit formation could not be prepared.

Comparative Example 5 (Circuit-forming film <9>) A circuit-forming film was formed in the same manner as in Example 1 except that the thickness of the non-adhesive resin layer having a layer thickness of less than 10 μm was changed to 15 μm. A photosensitive film <9> was produced.

Comparative Example 6 (Circuit-forming film <10>) In Example 1, the adhesive photosensitive resin layer material was changed to D-II.
A photosensitive film <10> for forming a circuit was prepared in the same manner as in Example 1 except that the above was adopted.

[Production of Printed Wiring Board A] Layer Thickness 35 μm
The copper surface of a glass epoxy substrate (trade name: MCL-E67-35S, manufactured by Hitachi Chemical Co., Ltd.) laminated with copper foil of
The copper clad laminate was obtained by polishing with a polishing machine (manufactured by Sankei Co., Ltd.) having a brush equivalent to 00, washing with water, and then drying with an air stream.

After heating the obtained copper-clad laminate to 80 ° C., a high temperature laminator (HLM-30 manufactured by Hitachi Chemical Co., Ltd.)
00) to the above substrate, and Examples 1 to 4 and Comparative 1 to
The photosensitive film for circuit formation <1> to <7> and <9> to <10> prepared in 6 is peeled off, the adhesive photosensitive resin layer is directed toward the substrate, and the supporting film side is touched with the roll. It was laminated in this way. The laminating roll speed at this time was 1.5 m / min, the laminating roll temperature was 110 ° C., and the roll cylinder pressure was 0.4 MPa.

After the lamination, the film is cooled to 23 ° C., and then the photosensitive films for circuit formation <1> to <7> and <9> to <10>.
The support film and the cushion layer of 1 were peeled off. At this time,
In the circuit-forming film <7>, the non-adhesive resin layer having a layer thickness of less than 10 μm and a part of the adhesive photosensitive layer were transferred to the support film and the cushion layer.

Next, a negative mask (stofer 21 step tablet, line width / space width 400/6
Negative mask with wiring pattern of ~ 400/47 (resolution, unit: μm), line width / space width is 6/400
Using a negative mask having a wiring pattern of ~ 47/400 (adhesion, unit: μm) and an exposure machine (model EXM-1201, mercury short arc lamp) manufactured by Oak Manufacturing Co., Ltd.,
The stopher 21-step step tablet was exposed with an energy amount such that the number of remaining step steps after development was 6.0.

Then, with a 1 wt% sodium carbonate aqueous solution (30 ° C.), the photosensitive films <1> to <6> for forming a circuit and
<9> to <10> were spray-developed (spray pressure: 0.18 MPa) for the development times shown in Table 4 to form a resist pattern on the substrate. The value of the minimum space width without developing residue of the obtained resist pattern was measured as the resolution, and the minimum resist width formed without causing meandering and chipping was measured as the adhesiveness. The results are shown in Table 3. . Note that the smaller this value, the better the resolution and adhesion.

[Production of Printed Wiring Board B] Copper clad having a resist pattern formed thereon in the same manner as in the production of printed wiring board A except that a negative mask having a line width / space width of 1,000 μm / 100 μm was used. A laminated board was obtained (using only photosensitive film <1> for circuit formation). The obtained substrate was immersed in 100 g / L ammonium persulfate aqueous solution (30 ° C.) 1
Dip for 30 minutes, and then peel the resist pattern with a peeling solution (3% by mass sodium hydroxide aqueous solution, 50 ° C., spray pressure: 0.18 MPa), and the recess depth is 1 to 15 μm.
A copper clad laminate having a m and a recess width of 100 μm was obtained.

After heating the obtained copper clad laminate to 80 ° C., a high temperature laminator (HLM-30 manufactured by Hitachi Chemical Co., Ltd.)
00) was used to form a photosensitive film for forming a circuit <1 on each of the above-mentioned substrates in Examples 1 to 4 and Comparative Examples 1 to 6.
<-><7> and <9>-<10> while peeling off the protective film, direct the adhesive photosensitive resin layer toward the substrate, and touch the support film side with the roll to laminate (laminate roll shaft and substrate The length direction of the wound was parallel). In addition,
Laminating roll speed is 1.5m / min, laminating roll temperature is 110 ° C, roll cylinder pressure is 0.4MP.
a.

Then, after the lamination is finished, the laminate is cooled to 23 ° C. and the photosensitive films for circuit formation <1> to <7> and <9> to <
The support film and cushion layer of 10> were peeled off. At this time, in the circuit-forming film <7>, part of the non-adhesive resin layer and the adhesive photosensitive resin layer having a layer thickness of less than 10 μm were transferred to the support film and the cushion layer.

Next, a negative mask (stofer 21 step tablet, line width / space width 100/1
Using a negative mask having a wiring pattern of 00 (unit: μm) and an exposure machine manufactured by Oak Manufacturing Co., Ltd. (model EXM-1201, mercury short arc lamp), the number of remaining step steps after development of the 21-step stoffer step tablet is 6 .0
It was exposed with the amount of energy.

Then, with a 1% by mass aqueous sodium carbonate solution (30 ° C.), the photosensitive films for circuit formation <1> to <6> and
<9> to <10> were spray-developed (spray pressure: 0.18 MPa) for the development times shown in Table 4 to form a resist pattern on the substrate.

Then, a cupric chloride etching solution (2 mol /
L CuCl ₂ , 2N-HCL aqueous solution, 50 ° C, spray pressure:
After spraying 0.2 MPa) for 100 seconds to dissolve the copper in the portion not protected by the resist, the resist pattern is stripped (3% by mass sodium hydroxide aqueous solution, 50% by mass).
C., spray pressure, spray pressure: 0.2 MPa), peeling was performed to produce a printed wiring board B having copper lines formed on the substrate.

When the laminated film does not follow the recesses on the substrate, since there is a gap between the resist and the substrate, the copper line dissolves in the etching solution at the intersection of the resist and the recesses. However, the copper line is not connected, resulting in disconnection failure. Scratch depth at which disconnection starts (unit: μ
m) is the unevenness followability (the larger this value, the better the followability), and the results are shown in Table 4. In Table 4, A
The layer is a support film, the B layer is a cushion layer, the C layer is a non-adhesive resin layer having a layer thickness of less than 10 μm, the D layer is an adhesive photosensitive resin layer, and the E layer is a protective film. Also,
The interlayer adhesive force is A that constitutes the photosensitive film for circuit formation.
It shows a portion having the smallest interlayer adhesive force among the layers, B layer, C layer, D layer and E layer.

[0121]

[Table 4] As shown in Table 4, circuit forming photosensitive films <1> to <4>
In each of Examples 1 to 4 using, the circuit-formed photosensitive film <5> in which the non-adhesive resin layer (C layer) was not formed, although there was no transfer to another material such as a substrate, In Comparative Example 1 used, transfer to another material occurred.

Comparative Example 2 using the circuit-forming photosensitive film <6> was prepared under the same conditions as in Example 1 except that the cushion layer of Example 1 was not formed. Although the resolution and the adhesiveness of No. 2 were about the same, in Example 1, the cushioning layer (B layer) was formed, so the followability was improved as compared with Example 1.

In Comparative Example 5, the circuit-forming photosensitive film <9> having a non-adhesive resin layer thickness of 10 μm or more was used, but the non-adhesive resin layer thickness was less than 10 μm. In Examples 1 and 3 using the photosensitive films <1> and <3> for forming a circuit, the resolution and the adhesion were excellent as compared with Comparative Example 5.

Furthermore, in Example 1 using the photosensitive film <1> for circuit formation, 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane was added to the adhesive photosensitive resin layer. Circuit forming photosensitive film not blended
Compared with <10>, the resolution and adhesion were excellent.

Therefore, according to this embodiment, for forming a circuit of the present invention, the cushion layer and the non-adhesive resin layer having a layer thickness of less than 10 μm are interposed between the support film and the adhesive photosensitive resin layer. By using the photosensitive film, not only the circuit-forming photosensitive film can be surely brought into close contact with the substrate to improve the followability, but also the resolution, the pattern accuracy and the manufacturing yield of the printed wiring board can be improved.

[0126]

As described above, according to the method of manufacturing the photosensitive film for forming a circuit and the printed wiring board of the present invention, the production cost when the photosensitive film is laminated on the substrate to be laminated so as to be in contact therewith. The transfer film can be transferred without causing transfer defects due to minute dust, air bubbles, unevenness of the substrate surface, etc. without raising the temperature, and the support film and cushion layer can be easily formed from a non-adhesive resin layer having a layer thickness of less than 10 μm. Since it can be peeled off, the resolution and the resist pattern accuracy are improved, and the manufacturing yield of the printed wiring board is greatly improved, which is extremely useful for increasing the density and resolution of the printed wiring board.

[Brief description of drawings]

FIG. 1 is an enlarged view showing a cross section of a photosensitive film for circuit formation in the present embodiment.

[Explanation of symbols]

1 Photosensitive film for circuit formation 2 Support film 3 cushion layers 4 Non-adhesive resin layer 5 Adhesive photosensitive resin layer 6 protective film

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takeshi Ohashi             Hitachi, Ichiba, Ibaraki Prefecture             Seikou Co., Ltd. Yamazaki Office F-term (reference) 2H025 AA02 AA04 AA14 AB11 AC01                       AD01 BC13 BC42 BC65 BC83                       CB13 CB16 CB55 DA40

Claims (16)

[Claims] 1. A support film, a cushion layer formed by sequentially laminating on the support film, and having a layer thickness of 10 μm.
a non-adhesive resin layer having a thickness of less than m and an adhesive photosensitive resin layer, and an interlayer adhesive force between the cushion layer and the non-adhesive resin layer is an interlayer adhesive force between the support film and the cushion layer; A photosensitive film for forming a circuit, which has a lower adhesive strength between the non-adhesive resin layer and the adhesive photosensitive resin layer. 2. A protective film is formed on the adhesive photosensitive resin layer on the side facing the non-adhesive resin layer having a layer thickness of less than 10 μm, and between the adhesive photosensitive resin layer and the protective film. 3. The photosensitive film for forming a circuit according to claim 1, wherein the interlayer adhesive strength of is less than the interlayer adhesive strength between the cushion layer and the non-adhesive resin layer having a layer thickness of less than 10 μm. 3. The adhesive photosensitive resin layer comprises (a) a binder polymer, (b) 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane, and (c) at least. 3. An adhesive photosensitive resin material containing at least one photopolymerizable compound having a polymerizable ethylenically unsaturated bond, and (d) a photopolymerization initiator. Photosensitive film for circuit formation. 4. The circuit according to claim 1, wherein the cushion layer is made of a material whose main component is a copolymer containing ethylene as an essential copolymerization component. Forming photosensitive film. 5. The EVA (ethylene-vinyl acetate copolymer) having a copolymerization ratio of ethylene of 60 to 90% by mass or the EEA (copolymerization ratio of ethylene of 60 to 90% by mass) of the copolymer. It is an ethylene-ethyl acrylate copolymer), The photosensitive film for circuit formation of Claim 4 characterized by the above-mentioned. 6. The photosensitive film for forming a circuit according to claim 1, wherein the layer thickness of the cushion layer is in the range of 1 μm to 100 μm. . 7. The binder polymer (a) contained in the adhesive photosensitive resin material forming the adhesive photosensitive resin layer contains methacrylic acid as an essential copolymerization component. 4. The photosensitive film for forming a circuit according to any one of 4, 5, and 6. 8. The circuit forming photosensitive material according to claim 3, wherein the acid value of the binder polymer (a) is 100 to 500 mgKOH / g. Sex film. 9. The mass average molecular weight of the (a) binder polymer is 20,000 to 300,000, and the binder polymer according to any one of claims 3, 4, 5, 6, 7 or 8. Photosensitive film for circuit formation. 10. The binder polymer (a) contains styrene or a styrene derivative as an essential copolymerization component, as claimed in claim 3, 4, 5, 6, 7, 8
Or the photosensitive film for forming a circuit according to any one of 9 to 9. 11. The binder polymer (a) comprises styrene or a styrene derivative in an amount of 0.
1-40 mass% is contained, The claim 3 characterized by the above-mentioned.
The photosensitive film for forming a circuit according to any one of 4, 5, 6, 7, 8, 9 or 10. 12. The 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane contained in the adhesive photosensitive resin material has the general formula (I): (In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, X ¹ and X ² each independently represent an alkylene group having 2 to 6 carbon atoms, and p and q are p + q = 4 to 40. A positive integer selected so that the compound represented by the formula (3) is a positive integer.
The photosensitive film for forming a circuit according to any of 10 or 11. 13. The photosensitive film for forming a circuit according to claim 12, wherein the X ¹ and X ² are ethylene groups. 14. The method according to claim 1, 2, 3, 4,
After laminating the circuit-forming photosensitive film according to any one of 5, 6, 7, 8, 9, 10, 11, 12, or 13 so that the adhesive photosensitive resin layer contacts the substrate,
A method for producing a printed wiring board, comprising: peeling off the support film and the cushion layer of the laminated photosensitive film for circuit formation, then exposing through a pattern mask and developing. 15. Claims 2, 3, 4, 5, 6, 7, 8,
9. After peeling off the protective film formed on the surface of the circuit-forming photosensitive film according to any one of 9, 10, 11, 12 or 13, the adhesive photosensitivity of the circuit-forming photosensitive film on the substrate. A method for manufacturing a printed wiring board, which comprises laminating a conductive resin layer so as to be in contact with the substrate, peeling off the supporting film and the cushion layer, exposing through a pattern mask, and developing. 16. The pattern mask is adhered onto a non-adhesive resin layer having a layer thickness of less than 10 μm after the support film and the cushion layer of the photosensitive film for circuit formation are peeled off. Claim 14 or 1
5. The method for manufacturing a printed wiring board according to 5.