JP2008250246A - Method for manufacturing photosensitive laminate, and printed wiring board and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: a method for manufacturing a photosensitive laminate showing favorable plating durability and developing property in which a high-definition pattern can be efficiently formed; a printed wiring board using the above photosensitive laminate; and a method for manufacturing the board. <P>SOLUTION: The method for manufacturing a photosensitive laminate includes a step of laminating a photosensitive layer comprising a photosensitive composition on the surface of a substrate having a surface roughness of 180 nm to 500 nm and a surface contamination degree of ≤4.0 mol%. A photosensitive laminate is obtained by the above method. The method for manufacturing a printed wiring board includes: a laminate forming step of forming a photosensitive laminate according to the above method; an exposure step of subjecting the photosensitive layer of the photosensitive laminate formed in the laminate forming step to pattern exposure; a developing step of removing an unexposed region in the photosensitive layer after the exposure step; and a curing step of curing the photosensitive layer after the developing step. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a photosensitive laminate having a permanent pattern (insulating film, coverlay, solder resist, etc.) excellent in plating resistance, a printed wiring board using the photosensitive laminate, and a method for producing the same.

  Conventionally, when producing a permanent pattern such as a solder resist pattern, in order to have good adhesion in the process of forming a laminate by laminating a photosensitive composition on a substrate, It incorporates a polishing process aimed at removing oxides and creating an active metal surface and roughening the surface of the wiring pattern in micro units.

  In the above polishing step, when the substrate or the wiring pattern surface is not sufficiently rough (for example, when having a glossy smooth surface), the photosensitive composition and the wiring pattern have sufficient adhesion. In the development process and electroless gold plating process, part or all of the area that should be protected may be peeled off, or liquid may be leaked at the interface between the substrate or the wiring pattern and the permanent pattern. May occur. In such a case, corrosion, a short circuit, etc. occur in the defective part, which may cause a fire from the printed wiring board.

  On the other hand, if the irregularities on the surface of the wiring pattern become too large, the adhesion to the metal surface is too strong, and even the unexposed part that should be dissolved and removed in the development process remains as a residue, mounting electronic components Sometimes bad. Accordingly, it is desired to form a permanent pattern having appropriate adhesion to the substrate and the wiring pattern surface.

On the other hand, for example, by spraying a basic polishing liquid containing alkanolamine onto the substrate, the metal surface can be polished by several μm, and the adhesion between the substrate surface and the resist ink and solderability can be improved. It is disclosed that it is excellent (for example, Patent Documents 1 and 2). However, the degree of contamination of the substrate surface with oxygen, nitrogen, etc. is not explained at all and is not taken into consideration.
Japanese Patent No. 3458036 JP 2001-200380 A

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention provides a method for producing a photosensitive laminate having good plating resistance and developability and capable of efficiently forming a high-definition pattern, a printed wiring board using the photosensitive laminate, and a method for producing the same. The purpose is to provide.

Means for solving the problems are as follows. That is,
<1> including a step of laminating a photosensitive layer made of a photosensitive composition on a substrate surface having a surface roughness of 180 nm to 500 nm and a surface contamination degree of 4.0 mol% or less. This is a method for producing a photosensitive laminate.
<2> The method for producing a photosensitive laminate according to <1>, wherein the photosensitive layer is formed by applying and drying the photosensitive composition on a substrate surface.
<3> A photosensitive film formed by laminating a photosensitive layer on a temporary support is overlapped so that the photosensitive layer is in contact with the substrate surface, and at least one of heating and pressurization is performed. The method for producing a photosensitive laminate according to <1>, wherein the photosensitive layer is transferred and laminated.
<4> Production of photosensitive laminate according to any one of <1> to <3>, wherein the base material is any one of a metal copper substrate and a substrate having at least one metal copper layer as at least one outermost layer. Is the method.
<5> The method for producing a photosensitive laminate according to any one of <1> to <4>, wherein the photosensitive composition includes at least a binder, a polymerizable compound, a photopolymerization initiator, and an inorganic filler. .
<6> A photosensitive laminate produced by the method according to any one of <1> to <5>.
<7> A laminate forming step of forming a photosensitive laminate by the method according to any one of <1> to <5>,
An exposure step for pattern exposure on the photosensitive layer of the photosensitive laminate formed in the laminate formation step;
After the exposure step, a development step for removing unexposed areas in the photosensitive layer;
And a curing step of further curing the photosensitive layer after the development step.
<8> A printed wiring board manufactured by the method according to <7>.

  According to the present invention, the conventional problems can be solved, the plating resistance and developability are good, and a method for producing a photosensitive laminate capable of efficiently forming a high-definition pattern, and the photosensitive laminate The used printed wiring board and the manufacturing method thereof can be provided.

(Photosensitive laminate)
The photosensitive laminate is formed by laminating at least the photosensitive layer on a substrate and other layers appropriately selected according to the purpose.

<Base material>
The base is not particularly limited as long as it has a convex portion, but a plate-like base (substrate) is preferable. Specifically, a known printed board (for example, a copper-clad laminate), a glass plate ( Examples thereof include soda glass plates), synthetic resin films, paper, metal plates, and the like.
The height of the convex portion is preferably about 0.5 to 2 μm from the viewpoint of improving the adhesion with the laminated photosensitive film.
There is no restriction | limiting in particular as a formation method of the said convex part, It can select suitably from a well-known method, For example, methods, such as chemical polishing, are mentioned.

  Preferred examples of the printed circuit board include a glass epoxy board, an epoxy-impregnated aramid nonwoven fabric, and a surface of an insulating layer such as polyimide and a copper foil layer provided as a plating foil or a sputtered foil. When the sputter foil is provided, another metal foil (Ni, Cr, etc.) may be provided as a base layer for the purpose of improving the adhesion between the copper foil and the insulating layer.

  In order to obtain sufficient adhesion between the substrate and the photosensitive layer, the surface roughness of the substrate is preferably 180 nm to 500 nm, and more preferably 200 nm to 450 nm. If it is less than 180 nm, the adhesion between the substrate and the photosensitive layer is lowered, and the plating resistance becomes insufficient. On the other hand, when the thickness exceeds 500 nm, the adhesion between the substrate and the photosensitive layer becomes too strong, and residues remain in unexposed portions during development, or etching takes time, resulting in poor productivity.

  The standard of surface roughness includes centerline average roughness (Ra), maximum height (Rmax), ten-point average height (Rz), etc., but “surface roughness” in the present invention refers to centerline Average roughness (Ra). The centerline average roughness (Ra) is a value obtained by folding the roughness curve from the centerline and dividing the area obtained by the roughness curve and the centerline by the length L in micrometers (μm). Generally, it is measured by a center line average roughness measuring device.

  Further, the “surface contamination degree” in the present invention is measured by the molar ratio (%) of the carbon element on the substrate surface. The surface contamination degree of the substrate is preferably low, for example, preferably 4.0 mol% or less, more preferably 3.0 mol% or less, and 2.5 mol% or less. Is particularly preferred. If it exceeds 4.0 mol%, the adhesion between the substrate and the photosensitive layer is lowered, and the plating resistance becomes insufficient.

<Photosensitive layer>
The photosensitive layer is made of a photosensitive composition.
[Photosensitive composition]
The photosensitive composition contains a binder, a polymerizable compound, a photopolymerization initiator, and an inorganic filler, and further contains other components as necessary.

-Binder-
The binder is a compound that has sufficient viscosity (for example, 1 × 10 ⁴ or less) to be embedded in the circuit pattern at the heating temperature at the time of lamination, and is soluble in alkali, that is, a compound that swells or dissolves in an alkaline aqueous solution. There is no particular limitation, and it can be appropriately selected according to the purpose. For example, re-published WO 00/68740, JP-A 2001-354885, JP-A 2004-300265, JP-A 2004-300305, Examples thereof include resins described in Japanese Unexamined Patent Publication No. 2005-316431. Moreover, the said binder may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  5-80 mass% is preferable and, as for solid content content in the said photosensitive composition of the said binder, 10-70 mass% is more preferable. If it is less than 5% by mass, the alkali developability and the adhesion to a printed wiring board forming substrate (for example, a copper-clad laminate) may be reduced, or the film strength of the photosensitive layer may be weakened. If it exceeds 1, the stability with respect to the development time, the strength of the cured film (tent film) may decrease, and the exposure sensitivity may decrease.

The acid value of the binder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 70 to 250 (mgKOH / g), more preferably 90 to 200 (mgKOH / g), 100 to 180 (mg KOH / g) is particularly preferable.
If the acid value is less than 70 (mgKOH / g), problems such as insufficient developability or poor resolution and a high-definition permanent pattern such as a wiring pattern may occur. If it exceeds 250 (mgKOH / g), at least one of the developer resistance and adhesion of the pattern may deteriorate, and a permanent pattern such as a wiring pattern may not be obtained with high definition.

-Polymerizable compound-
The polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. However, the polymerizable compound has at least one addition-polymerizable group in the molecule and has a boiling point of 100 ° C. or higher at normal pressure. A compound is preferable, for example, at least 1 sort (s) selected from the monomer which has a (meth) acryl group is mentioned suitably. In the present invention, the “polymerizable compound” does not include a polymerizable compound that can be contained in the binder.

  There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) ) Monofunctional acrylates and monofunctional methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentylglycol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin Poly (functional) alcohols such as tri (meth) acrylate, trimethylolpropane, glycerin, bisphenol, etc., which are subjected to addition reaction with ethylene oxide and propylene oxide, and converted to (meth) acrylate, Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50- Urethane acrylates described in JP-A-6034, JP-A-51-37193, etc .; JP-A-48-64183, JP-B-49-43191, JP-B-52-30 Polyester acrylates described in each publication of such 90 No.; and epoxy resin and (meth) polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of acrylic acid. Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable. The said polymeric compound may be used individually by 1 type, and may use 2 or more types together. Examples of commercially available products obtained by subjecting polyfunctional alcohols such as bisphenol to (meth) acrylate after addition reaction of ethylene oxide or propylene oxide include BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.). It is done.

  5-50 mass% is preferable and, as for solid content in the said photosensitive composition solid content of the said polymeric compound, 10-40 mass% is more preferable. If the solid content is less than 5% by mass, problems such as deterioration of developability and reduction in exposure sensitivity may occur, and if it exceeds 50% by mass, the adhesiveness of the photosensitive layer may become too strong. Yes, not preferred.

-Photopolymerization initiator-
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is visible from the ultraviolet region. It is preferable to have photosensitivity to the light, and it may be an activator that produces some kind of action with a photoexcited sensitizer and generates an active radical. Initiator may be used.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a wavelength range of about 300 to 800 nm. The wavelength is more preferably 330 to 500 nm.

  Examples of other photopolymerization initiators include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), hexaarylbiimidazoles, organic peroxides, thio compounds, ketones. Examples thereof include compounds, acridine compounds, metallocenes, oxime ester compounds and the like. Specific examples include compounds described in JP-A-2005-311305. Among these, ketone compounds and acridine compounds are preferable from the viewpoints of sensitivity of the photosensitive layer, storage stability, and adhesion between the photosensitive layer and the substrate. The said other photoinitiator may be used individually by 1 type, and may use 2 or more types together.

  The solid content of the photopolymerization initiator in the photosensitive composition is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 0.5 to 15% by mass. .

-Inorganic filler-
The inorganic filler can improve the surface hardness of the pattern, can keep the coefficient of linear expansion low, and can keep the dielectric constant and dielectric loss tangent of the photosensitive layer itself low. It can be used suitably.
The inorganic filler is not particularly limited and may be appropriately selected depending on the intended purpose. For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, gas phase method silica, amorphous Examples include silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica and the like.

The average particle size of the inorganic filler is preferably less than 3 μm, more preferably 0.1 μm to 2 μm. If the average particle size is 3 μm or more, resolution may be deteriorated due to light scattering.
The addition amount of the inorganic filler is preferably 5% by mass to 75% by mass, more preferably 8% by mass to 70% by mass, and particularly preferably 10% by mass to 65% by mass. If it is less than 5% by mass, the linear expansion coefficient may not be sufficiently reduced. If it exceeds 75% by mass, when the photosensitive layer is cured, the film quality of the cured film becomes brittle, and the wiring becomes In the case of formation, the function as a protective film for wiring may be impaired.

Furthermore, organic fine particles can be added as necessary. There is no restriction | limiting in particular as said organic fine particle, According to the objective, it can select suitably, For example, a melamine resin, a benzoguanamine resin, a crosslinked polystyrene resin etc. are mentioned. It is also possible to use an average particle diameter of 0.1-2 .mu.m, oil absorption 100m ² / g~200m ² / g approximately silica, spherical porous fine particles composed of a crosslinked resin.

-Other ingredients-
Examples of the other components include a thermal crosslinking agent, a sensitizer, a thermal polymerization inhibitor, a plasticizer, a colorant (color pigment or dye), and further an adhesion promoter for the substrate surface and other components. Auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension adjusting agents, chain transfer agents, etc.) may be used in combination. By appropriately containing these, properties such as the stability, photographic properties, and film properties of the intended photosensitive film can be adjusted.

--- Thermal crosslinking agent-
The photosensitive composition preferably further contains a thermal crosslinking agent. The thermal crosslinking agent is not particularly limited and may be appropriately selected depending on the purpose. In order to improve the film strength after curing of the photosensitive layer formed using the photosensitive film, developability, etc. For example, an epoxy compound having at least two oxirane groups in one molecule and at least two oxetanyl groups in one molecule described in JP-A No. 2005-311305 Oxetane compounds, polyisocyanate compounds, blocked isocyanate compounds, and melamine derivatives having

  1-50 mass% is preferable and, as for solid content in the said photosensitive composition solid content of the said thermal crosslinking agent, 3-30 mass% is more preferable. When the solid content is less than 1% by mass, improvement in the film strength of the cured film is not recognized, and when it exceeds 50% by mass, developability and exposure sensitivity may be deteriorated.

--- Sensitizer--
The photosensitive composition preferably further contains a sensitizer. The sensitizer is used in combination when the photosensitive layer is exposed and developed to improve the minimum energy (sensitivity) of the light that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development. It is particularly preferred.
The sensitizer can be appropriately selected according to the light irradiation means (for example, visible light, ultraviolet light, visible light laser, etc.).
The sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby generating radicals, acids, etc. It is possible to generate a useful group of
The sensitizer is at least one selected from condensed ring compounds, aminophenyl ketone compounds, polynuclear aromatics, those having an acidic nucleus, those having a basic nucleus, and those having a fluorescent brightener nucleus. It contains seeds and may contain other sensitizers as needed. As the sensitizer, a hetero-fused compound and an aminobenzophenone compound are further preferable from the viewpoint of improving sensitivity, and a hetero-fused compound is particularly preferable.

The content of the sensitizer is preferably 0.01 to 4% by mass, more preferably 0.02 to 2% by mass, and 0.05 to 1% by mass with respect to the total solid content of the photosensitive composition. Particularly preferred.
When the content is less than 0.01% by mass, the sensitivity may decrease, and when it exceeds 4% by mass, the shape of the pattern may be deteriorated.

The mass ratio of the sensitizer and the content of the photopolymerization initiator in the photosensitive composition is [(sensitizer) / (photopolymerization initiator)] = 1 / 0.1 to 1/100. It is preferable that the ratio is 1/1 to 1/50.
When the mass ratio between the content of the sensitizer and the content of the photopolymerization initiator is outside the above range, the sensitivity may be lowered and the change in sensitivity over time may be deteriorated.

When the photosensitive layer formed of the photosensitive composition is exposed and developed, the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is: is preferably ^{0.1mJ / cm 2 ~200mJ / cm 2} , more preferably from ^{0.2mJ / cm 2 ~100mJ / cm 2} , to be 0.5mJ / cm ² ~50mJ / cm 2 Particularly preferred.
The minimum energy is less than 0.1 mJ / cm ^2, may fogging in process step occurs, it exceeds 200 mJ / cm ^2, increases the time necessary for exposure, processing speed is slow Sometimes.

Here, the “minimum energy of light used for the exposure in which the thickness of the exposed portion of the photosensitive layer is not changed after the exposure and development” (hereinafter may be simply referred to as “minimum energy of light”). The so-called development sensitivity, for example, the relationship between the amount of energy (exposure amount) of light used for the exposure when the photosensitive layer is exposed and the thickness of the cured layer generated by the development process following the exposure It can obtain | require from the graph (sensitivity curve).
The thickness of the cured layer increases as the amount of exposure increases, and then becomes substantially the same and substantially constant as the thickness of the photosensitive layer before the exposure. The development sensitivity is a value obtained by reading the minimum exposure when the thickness of the cured layer becomes substantially constant.
Here, when the difference between the thickness of the cured layer and the thickness of the photosensitive layer before the exposure is within ± 1 μm, it is considered that the thickness of the cured layer is not changed by exposure and development.
A method for measuring the thickness of the cured layer and the photosensitive layer before exposure is not particularly limited and may be appropriately selected depending on the intended purpose. However, a film thickness measuring device, a surface roughness measuring machine (for example, Surfcom) 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)) and the like.

Further, the variation rate (%) of the minimum energy of light in light having a wavelength of 400 nm to 410 nm (hereinafter also referred to as “sensitivity variation”) is preferably within 20%. If the variation rate exceeds 20%, the pattern shape in the surface may vary.
Here, for example, after measuring the minimum energy of the light in a light having a wavelength of 400 nm, the variation rate is measured by sequentially measuring the minimum energy of the light up to a light having a wavelength of 410 nm by shifting the wavelength by 1 nm. From the difference between the maximum value (Emax) and the minimum value (Emin) of the minimum energy, the following equation can be used.
〔formula〕
(Emax-Emin) / Emax

  There is no restriction | limiting in particular in the thickness of the said photosensitive layer, Although it can select suitably according to the objective, For example, 10-100 micrometers is preferable, 20-50 micrometers is more preferable, 25-45 micrometers is especially preferable.

(Method for producing photosensitive laminate)
There is no restriction | limiting in particular as a manufacturing method of the said photosensitive laminated body, Although it can select suitably according to the objective, As a 1st aspect, the photosensitive composition is apply | coated and dried to the said base-material surface, and photosensitive. The method of forming a layer is mentioned, and as a second aspect, a photosensitive film in which a photosensitive layer is laminated on the temporary support is stacked so that the photosensitive layer is in contact with the substrate surface, and heated and pressed. And a method of transferring and laminating the photosensitive layer on the substrate surface.

<First aspect>
In the manufacturing method of the photosensitive laminated body of the said 1st aspect, a photosensitive composition is apply | coated and dried on the said base-material surface, and a photosensitive layer is formed.
The coating and drying method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the photosensitive composition is dissolved, emulsified or dispersed on the surface of the base material in water or a solvent. And a method of laminating by preparing a photosensitive composition solution, applying the solution directly, and drying the solution.

  There is no restriction | limiting in particular as a solvent of the said photosensitive composition solution, According to the objective, it can select suitably, For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol Alcohols such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, etc .; ethyl acetate, butyl acetate, acetic acid-n-amyl, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and Esters such as methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; halo such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, monochlorobenzene Emissions of hydrocarbons; tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethers such as 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and sulfolane. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

  The method for coating and drying is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the photosensitive composition solution may be spin coater, slit spin coater, roll coater, die coater, curtain coater, etc. The method of apply | coating using is mentioned.

<Second aspect>
In the method for producing a photosensitive laminate of the second aspect, a photosensitive film in which a photosensitive layer is laminated on the temporary support is overlaid so that the photosensitive layer is in contact with the substrate surface, and heated and pressed. Then, the photosensitive layer is transferred and laminated on the substrate surface. In addition, when the said photosensitive film has a protective layer, it is preferable to peel this protective layer and to laminate | stack so that the said photosensitive layer may overlap with the said base material.
There is no restriction | limiting in particular as said heating temperature, Although it can select suitably according to the objective, For example, 70 to 130 degreeC is preferable and 80 to 110 degreeC is more preferable.
There is no restriction | limiting in particular as a pressure of the said pressurization, Although it can select suitably according to the objective, For example, 0.01 MPa-1.0 MPa are preferable and 0.05 MPa-1.0 MPa are more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating and pressurization, According to the objective, it can select suitably, For example, heat press, a heat roll laminator (For example, Taisei Laminator company make, VP-II) ), A vacuum laminator (for example, MVLP500 manufactured by Meiki Seisakusho, VP130 manufactured by Nichigo Morton Co., Ltd.) and the like are preferable.

  The photosensitive laminate of the present invention has good sensitivity, developability, and adhesion, and can efficiently form a high-definition pattern, such as a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist pattern. It can be suitably used for various pattern formation, color filter, pillar material, rib material, spacer, manufacturing liquid crystal structural members such as partition walls, holograms, micromachines, proofs, etc., especially for printed circuit boards. It can be suitably used for pattern formation.

[Photosensitive film]
The photosensitive film used in the method for producing a photosensitive laminate of the second aspect is not particularly limited as long as it has at least the photosensitive layer on a temporary support, and is appropriately selected according to the purpose. be able to. The photosensitive layer is preferably formed on a temporary support, and a cushion layer may be provided between the support and the photosensitive layer, or a protective film may be formed on the photosensitive layer. . Furthermore, other layers appropriately selected may be provided.

-Temporary support-
The temporary support is not particularly limited as long as the photosensitive layer can be peeled off, and can be appropriately selected according to the purpose. However, a material having good surface smoothness is preferable, and light transmittance is good. Those having good are particularly preferred.

  The temporary support is preferably made of synthetic resin, for example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly (meth) acrylic. Acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulose Examples thereof include various plastic films such as a polyethylene film and a nylon film, and among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.

  The thickness of the temporary support is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 2 μm to 150 μm, more preferably 5 μm to 100 μm, and particularly preferably 8 μm to 50 μm. The temporary support may be a single layer, or may have a multilayer structure as described in, for example, republished WO 00/79344 and JP-A-2005-77646.

  There is no restriction | limiting in particular as a shape of the said temporary support body, Although it can select suitably according to the objective, A long shape is preferable. The length of the long temporary support is not particularly limited, and examples thereof include a length of 10 m to 20,000 m.

-Other layers-
There is no restriction | limiting in particular as said other layer, According to the objective, it can select suitably, For example, layers, such as a protective layer, a cushion layer, a barrier layer, a peeling layer, an adhesive layer, a light absorption layer, a surface protective layer Is mentioned. The said pattern formation material may have these layers individually by 1 type, and may have 2 or more types. Moreover, you may have 2 or more of the same kind of layers.

--Protective layer--
The photosensitive film may form a protective layer on the photosensitive layer.
Examples of the protective layer include those used for the temporary support, paper, polyethylene, and paper laminated with polypropylene. Among these, polyethylene film and polypropylene film are preferable.
There is no restriction | limiting in particular in the thickness of the said protective layer, Although it can select suitably according to the objective, For example, 5 micrometers-100 micrometers are preferable, 8 micrometers-50 micrometers are more preferable, 10 micrometers-30 micrometers are especially preferable.
Examples of the combination of the temporary support and the protective layer (temporary support / protective layer) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. Can be mentioned. Moreover, interlayer adhesion can be adjusted by surface-treating at least one of the temporary support and the protective layer. The surface treatment of the temporary support may be performed to increase the adhesive force with the photosensitive layer, for example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high-frequency irradiation treatment, Examples include glow discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.

Moreover, 0.3-1.4 are preferable and the static friction coefficient of the said support body and the said protective film has more preferable 0.5-1.2.
When the coefficient of static friction is less than 0.3, slipping is excessive, so that winding deviation may occur when the roll is formed, and when it exceeds 1.4, it is difficult to wind into a good roll. Sometimes.

  The protective layer may be surface-treated to adjust the adhesion between the protective layer and the photosensitive layer. Examples of the surface treatment include a treatment for forming an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol on the surface of the protective layer. The undercoat layer can be formed by applying the polymer coating solution on the surface of the protective layer and then drying at 30 ° C. to 150 ° C. for 1 to 30 minutes. The drying temperature is particularly preferably 50 ° C to 120 ° C.

  For example, the photosensitive film is preferably wound around a cylindrical core, wound into a long roll, and stored. The length of the long photosensitive film is not particularly limited, and can be, for example, 10 m to 20,000 m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 m to 1,000 m may be formed into a roll. In this case, it is preferable that the temporary support is wound up so as to be the outermost side. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. From the viewpoint of protecting the end face and preventing edge fusion during storage, it is preferable to install a separator (especially moisture-proof and desiccant-containing) on the end face, and use a low moisture-permeable material for packaging. It is preferable.

The said photosensitive film can be manufactured as follows, for example.
First, the material contained in the photosensitive composition is dissolved, emulsified or dispersed in water or a solvent to prepare a photosensitive composition solution for a photosensitive film.

  There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol; acetone , Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate Aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, monochlorobenzene; Tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethers such as 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and sulfolane. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

  Next, the photosensitive composition solution is applied on the temporary support and dried to form a photosensitive layer.

The method for applying the photosensitive composition solution is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a spray method, a roll coating method, a spin coating method, a slit coating method, and an extrusion coating method. And various coating methods such as a curtain coating method, a die coating method, a gravure coating method, a wire bar coating method, and a knife coating method.
The drying condition varies depending on each component, the type of solvent, the use ratio, and the like, but is usually about 60 seconds to 110 ° C. for about 30 seconds to 15 minutes.

<Exposure process>
The said exposure process is a process of exposing with respect to the photosensitive layer of the said laminated body. The materials for the photosensitive layer and the substrate are as described above.
The exposure target is not particularly limited as long as it is the photosensitive layer, and can be appropriately selected according to the purpose. For example, as described above, the exposure is performed on the photosensitive layer on the substrate. It is preferable. At this time, exposure may be performed after peeling off the temporary support as necessary (for example, when the light transmittance of the temporary support is insufficient).

There is no restriction | limiting in particular as said exposure, According to the objective, it can select suitably, Digital exposure, analog exposure, etc. are mentioned, Among these, digital exposure is preferable.
The analog exposure is not particularly limited and can be appropriately selected depending on the purpose. For example, exposure with a (super) high pressure mercury lamp, xenon lamp, halogen lamp, etc. through a photomask having a predetermined pattern. The method of performing is mentioned.

  The digital exposure is not particularly limited as long as it is performed without using the photomask, and can be appropriately selected according to the purpose. For example, an exposure head including at least a light irradiation unit and a light modulation unit; The exposure head irradiates the photosensitive layer with light emitted from the light irradiation means while modulating at least one of the photosensitive layers according to pattern information by the light modulation means. It is preferable.

  The light source used in the digital exposure is not particularly limited as long as it is a light source that emits ultraviolet to near infrared rays, and can be appropriately selected according to the purpose. For example, (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp , Fluorescent lamps for use in halogen lamps and copying machines, or known light sources such as laser light are used. Among these, (ultra) high pressure mercury lamps and laser light are preferable, and laser light is more preferable.

  The (super) high pressure mercury lamp is a discharge lamp in which mercury is enclosed in a quartz glass tube or the like, and has a higher vapor pressure to increase luminous efficiency. Among the emission line spectra, an emission line spectrum of only one wavelength may be used using an ND filter or the like, or a light beam having a plurality of emission line spectra may be used.

The “laser” of the laser light is an acronym for Light Amplification by Stimulated Emission of Radiation. As an apparatus for emitting the laser light, an oscillator and an amplifier that generate monochromatic light having a higher coherence and directivity by amplification and oscillation of light waves using a phenomenon of stimulated emission that occurs in a material having an inversion distribution is preferably used. Can be mentioned.
Examples of the laser light excitation medium include crystals, glass, liquid, pigment, gas, and the like, and known lasers such as a solid laser, a liquid laser, a gas laser, and a semiconductor laser can be used.

Specifically, examples of the gas laser include an Ar ion laser (364 nm, 351 nm), a Kr ion laser (356 nm, 351 nm), and a He—Cd laser (325 nm), and examples of the solid laser include a YAG laser and a YVO ₄ laser (1, 064 nm), YAG laser or YVO ₄ laser, 2nd harmonic (532 nm), 3rd harmonic (355 nm), 4th harmonic (266 nm), a combination of a waveguide wavelength conversion element and an AlGaAs or InGaAs semiconductor (380 nm to 400 nm) ), A combination of a waveguide wavelength conversion element and an AlGaInP or AlGaAs semiconductor t (300 nm to 350 nm), AlGaInN (350 nm to 470 nm), and the like. Among these, suitable laser light includes an AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 375 nm or 405 nm) in terms of cost, and a 355 nm laser having high output in terms of productivity.

  The wavelength of the laser beam is, for example, preferably 200 to 1,500 nm, more preferably 300 to 800 nm, still more preferably 330 to 500 nm, and particularly preferably 350 to 420 nm.

-Light modulation means-
As the light modulation means, a typical method is a method having n pixel parts and controlling the pixel parts according to the pattern information. Specifically, a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulator (SLM), an optical element (PLZT element) that modulates transmitted light by an electro-optic effect. And liquid crystal light shutter (FLC). Among these, DMD is preferable.

When the DMD is used, light from a light source is irradiated onto the DMD by an appropriate optical system, and reflected light from each mirror arranged two-dimensionally on the DMD is exposed to light through another optical system. An image of light spots arranged in two dimensions is formed on the layer. In this state, the light spot is not exposed between the light spots. However, if the image of the light spots arranged in two dimensions is moved in a direction slightly inclined with respect to the two-dimensional arrangement direction, the light spots in the first row are used. The light spot in the rear row exposes between the light spot and the light spot, so that the entire surface of the photosensitive layer can be exposed. The DMD can form an image pattern by controlling the angle of each mirror and controlling the light spot on and off. By aligning and using such exposure heads having the DMD, it is possible to deal with substrates of various widths.
In the DMD, the brightness of the light spot has only two gradations, ON or OFF, but exposure with 256 gradations can be performed using a mirror gradation type spatial modulation element.

Moreover, it is preferable that the said light modulation means has a pattern signal generation means which produces | generates a control signal based on the pattern information to form. In this case, the light modulation unit modulates light according to the control signal generated by the pattern signal generation unit.
There is no restriction | limiting in particular as said control signal, According to the objective, it can select suitably, For example, a digital signal is mentioned suitably.

  On the other hand, another typical method of the light modulation means is a method using a polygon mirror. Here, the polygon mirror is a rotating member having a series of plane reflecting surfaces around it. The polygon mirror reflects and irradiates light from the light source onto the photosensitive layer, and the light spot of the reflected light is scanned by the rotation of the plane mirror. By moving the substrate at right angles to the scanning direction, the entire surface of the photosensitive layer on the substrate can be exposed. Then, an image pattern can be formed by controlling the intensity of light from the light source to ON-OFF or halftone by an appropriate method. At this time, the scanning time can be shortened by using a plurality of lights from the light source.

  As the light modulation means of the present invention, in addition, an example of drawing using a polygon mirror described in JP-A-5-150175, as described in JP-T-2004-523101 (International Publication No. 2002/039793 pamphlet). An example in which a part of the image of the lower layer is visually acquired, and exposure is performed by aligning the position of the upper layer with the position of the lower layer with an apparatus using a polygon mirror, and exposure with the DMD described in JP-A-2004-56080 For example, an exposure apparatus provided with a polygon mirror described in JP-T-2002-523905, an exposure apparatus provided with a polygon mirror described in JP-A-2001-255661, DMD, LD, and multiple exposure described in JP-A-2003-50469 An example of a combination of an exposure method in which the exposure amount is changed depending on the part of the substrate described in Japanese Patent Application Laid-Open No. 2003-156853 , Etc. Examples of an exposure method for performing a positional deviation adjustment described in JP 2005-43576 Publication and the like.

-Light irradiation means-
There is no restriction | limiting in particular as said light irradiation means, ie, the light irradiation method, Although the above-mentioned exposure light source can be suitably selected according to the objective, Two or more light from these light sources is synthesize | combined and irradiated. It is particularly preferable to irradiate a laser beam (combined laser beam) obtained by combining two or more lights.

  There is no restriction | limiting in particular as the irradiation method of the said combined laser beam, Although it can select suitably according to the objective, A laser irradiated from a several laser light source, a multimode optical fiber, and this several laser light source A method of composing and irradiating a combined laser beam with a collective optical system that collects light and couples it to the multimode optical fiber is preferable.

The beam diameter of the laser light is not particularly limited and may be appropriately selected depending on the purpose. From the viewpoint of the resolution of the dark color separation partition wall, the Gaussian beam 1 / e ² value is preferably 5 to 30 μm, 7-20 micrometers is more preferable.
In the present invention, it is preferable to spatially modulate laser light according to image data. Therefore, it is preferable to use the DMD which is a spatial light modulator for this purpose.

  Examples of the exposure apparatus having the light modulating unit and the light irradiating unit are described in JP-A-2005-222039, JP-A-2005-311305, JP-A-2006-30966, and the like. However, the exposure apparatus in the present invention is not limited to this.

<Development process>
The developing step is a step of removing an unexposed portion of the photosensitive layer.
There is no restriction | limiting in particular as the removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.

  There is no restriction | limiting in particular as said developing solution, Although it can select suitably according to the objective, For example, alkaline aqueous solution, an aqueous developing solution, an organic solvent etc. are mentioned, Among these, weakly alkaline aqueous solution is preferable. Examples of the basic component of the weak alkaline aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, phosphorus Examples include potassium acid, sodium pyrophosphate, potassium pyrophosphate, and borax.

For example, the pH of the weakly alkaline aqueous solution is preferably about 8 to 12, and more preferably about 9 to 11. Examples of the weak alkaline aqueous solution include a 0.1 to 5% by mass aqueous sodium carbonate solution or an aqueous potassium carbonate solution.
The temperature of the developer can be appropriately selected according to the developability of the photosensitive layer, and is preferably about 25 to 40 ° C., for example.

  The developer includes a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) and development. Therefore, it may be used in combination with an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.). The developer may be an aqueous developer obtained by mixing water or an aqueous alkali solution and an organic solvent, or may be an organic solvent alone.

<Curing process>
When the pattern formation method is a permanent pattern formation method for forming a permanent pattern such as a protective film, an interlayer insulating film, a solder resist pattern, or a color filter, the photosensitive layer is cured after the development step. It is preferable to provide the hardening process process which processes.
There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the development. The entire surface exposure accelerates the curing of the resin in the photosensitive composition forming the photosensitive layer, and the surface of the permanent pattern is cured.
An apparatus for performing the entire surface exposure is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a UV exposure machine such as an ultra-high pressure mercury lamp, an exposure machine using a xenon lamp, a laser exposure machine and the like are preferable. It is mentioned in. The exposure amount is usually 10 to 2,000 mJ / cm ² .

Examples of the whole surface heat treatment method include a method of heating the entire surface of the laminate on which the permanent pattern is formed after the development. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
120-250 degreeC is preferable and the heating temperature in the said whole surface heating has more preferable 120-200 degreeC. When the heating temperature is less than 120 ° C., the film strength may not be improved by heat treatment. When the heating temperature exceeds 250 ° C., the resin in the photosensitive composition is decomposed, and the film quality is weak and brittle. Sometimes.

The heating time in the entire surface heating is preferably 10 to 120 minutes, and more preferably 15 to 60 minutes.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

  The pattern forming method can be used for forming various patterns that require prevention of sensitivity reduction of the photosensitive layer by oxygen in direct writing by laser exposure of 405 nm, and has high density and high productivity. It can be suitably used for forming a compatible pattern.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
(Synthesis Example 1)
-Synthesis of binder 1-
In a 1,000 mL three-necked flask, 159 g of 1-methoxy-2-propanol was placed and heated to 85 ° C. under a nitrogen stream. To this, a solution of 159 g of 1-methoxy-2-propanol containing 63.4 g of benzyl methacrylate, 72.3 g of methacrylic acid, and 4.15 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped over 2 hours. After completion of the dropwise addition, the reaction was continued by heating for 5 hours to obtain a copolymer of benzyl methacrylate / methacrylic acid (ratio of 30/70 mol%).
120.0 g of the obtained copolymer solution was transferred to a 300 mL three-necked flask, 16.6 g of glycidyl methacrylate and 0.16 g of p-methoxyphenol were added, and the mixture was stirred and dissolved. After dissolution, 3.0 g of triphenylphosphine was added and heated to 100 ° C. to carry out an addition reaction. The disappearance of glycidyl methacrylate was confirmed by gas chromatography, and heating was stopped. 1-Methoxy-2-propanol was added to obtain a solution of binder 1 having an acid value of 112 mgKOH / g, a weight average molecular weight of 15,000 and a solid content of 30% by weight.

Example 1
-Preparation of photosensitive composition-
Each component was mix | blended in the following quantity and the photosensitive composition solution 1 was prepared.
[Each component amount of photosensitive composition solution 1]
-Solution of the binder 1 (solid content 30% by mass) ... 87.4 parts by mass-Dipentaerythritol hexaacrylate (polymerizable compound) ... 13.0 parts by mass-Represented by the following formula I-1 Photopolymerization initiator: 2.6 parts by mass Epototo YD-8125 (thermal crosslinking agent) (epoxy equivalent: 170 g / eq. Manufactured by Toto Kasei Co., Ltd., bisphenol A epoxy resin): 8.0 parts by mass Barium sulfate (manufactured by Sakai Chemical Co., Ltd., B30) 21.98 parts by mass Sensitizer represented by the following formula S-1 0.5 parts by mass Dicyandiamide (thermosetting agent) 0.77 parts by mass · Fluorosurfactant (Megafac F-176, manufactured by Dainippon Ink & Chemicals, 30% by weight 2-butanone solution) ··· 0.2 parts by mass · Methyl ethyl ketone ··· 15 .0 parts by mass

-Production of photosensitive laminates-
The photosensitive composition solution 1 is placed on a copper-clad laminate (surface roughness 205 nm, surface contamination degree 3.4 mol%) on which wiring has been formed as a printed circuit board by screen printing. Using a 120 mesh Tetron screen, it was applied to a thickness of 30 μm after drying, and dried at 80 ° C. for 15 minutes with a hot air circulation dryer to form a photosensitive layer. The copper clad laminate, the photosensitive layer The photosensitive laminated body by which the layer was laminated | stacked in this order was prepared.

In addition, the measuring method of the surface roughness of the said base material and a surface contamination degree is as follows.
<Surface roughness (nm)>
Measured with an atomic force microscope (AFM) (SPA500, DFM mode, measuring area 20 × 20 μm, probe DS-40P manufactured by Seiko Instruments Inc.).

<Surface contamination degree (mol%)>
Measured by surface elemental analysis (ESAC) (Shimadzu Axis-His).
(Wide measurement: 0-1100Ev, PE160, Step1, D-time100, CB2.3)
(Narrow measurement: PE40, Step0.1, D-time100, CB2.3)

The photosensitive laminate was evaluated for plating resistance and developability as follows. The results are shown in Table 1.
<Plating resistance>
Using the photosensitive laminate, INPREX IP-3000 (manufactured by FUJIFILM Corporation, pixel pitch = 1.0 μm), L / S (line / space) = line pattern data of 10 rows of 50 μm / 50 μm are arranged. Pattern exposure was performed by irradiation at 40 mJ / cm ² . This exposure amount is an amount of light energy sufficient to cure the photosensitive layer of the photosensitive film. After standing at room temperature for 10 minutes, the PET film was peeled off from the photosensitive laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. was sprayed onto the entire surface of the photosensitive layer on the copper clad laminate at a spray pressure of 0.15 MPa. Sprayed for 60 seconds to dissolve and remove uncured regions, washed with water and dried to form a pattern on the surface of the photosensitive layer.
After degreasing the surface of the photosensitive layer and roughening the surface, palladium sulfate was added to add a catalyst. Next, after plating for 40 minutes in a 70 ° C. nickel sulfate / dilute sulfuric acid solution, the pattern-cured film was turned up and peeled off visually and evaluated for plating resistance based on the following criteria. Went. The results are shown in Table 1.
〔Evaluation criteria〕
◎: Turned over to the cured film, without peeling, and extremely excellent plating resistance ○: Discolored part of the cured film, but no problem in practical use, excellent plating resistance △: Slightly turned over to the cured film There is no problem in practical use. X: The cured film is turned over and the plating resistance is inferior. Xx: Floating (peeling) is observed in the cured film, and the plating resistance is extremely inferior.

<Developability>
Immediately after producing the laminate, the PET film was peeled off from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. was sprayed at a pressure of 0.15 MPa over the entire surface of the photosensitive layer on the copper clad laminate. The time required from the start of spraying of the aqueous sodium solution until the photosensitive layer on the copper-clad laminate was dissolved and removed was measured, and this was defined as developability. When the photosensitive layer could not be removed even after 40 seconds of spray development at the time of measurement, it was evaluated as “x”.

-Production of photosensitive film-
The obtained photosensitive composition solution 1 was applied as a temporary support to a PET (polyethylene terephthalate) film (manufactured by Toray Industries, Inc., 16FB50) having a thickness of 16 μm, a width of 300 mm, and a length of 200 m using a bar coater. It dried in the hot-air circulation type dryer, and formed the photosensitive layer with a thickness of 30 micrometers. Next, a polypropylene film (E-200, manufactured by Oji Paper Co., Ltd.) having a thickness of 20 μm, a width of 310 mm, and a length of 210 m was laminated on the photosensitive layer as a protective layer by lamination to produce a photosensitive film.

(Example 2)
-Production of photosensitive laminates-
As the base material, a copper-clad laminate (surface roughness 205 nm, surface contamination degree 3.4 mol%) on which a wiring was formed as a printed board was prepared. The protective layer of the photosensitive film is peeled off, stacked so that the photosensitive layer of the photosensitive film is in contact with the copper-clad laminate, and laminated using a vacuum laminator (Nichigo Morton, VP130), and the copper-clad laminate A photosensitive laminate in which a plate, the photosensitive layer, and the polyethylene terephthalate film (temporary support) were laminated in this order was prepared.
The pressure bonding conditions were a vacuum drawing time of 40 seconds, a pressure bonding temperature of 70 ° C., a pressure bonding pressure of 0.2 MPa, and a pressure application time of 10 seconds.

(Example 3)
In Example 2, the plating resistance and developability were evaluated in the same manner except that the substrate was replaced with a copper-clad laminate (surface roughness 240 nm, surface contamination degree 1.9 mol%). The results are shown in Table 1.

(Comparative Example 1)
In Example 2, the plating resistance and developability were evaluated in the same manner except that the substrate was replaced with a copper-clad laminate (surface roughness 167 nm, surface contamination degree 1.5 mol%). The results are shown in Table 1.

(Comparative Example 2)
In Example 2, the plating resistance and developability were evaluated in the same manner except that the substrate was replaced with a copper-clad laminate (surface roughness 183 nm, surface contamination degree 1.8 mol%). The results are shown in Table 1.

(Comparative Example 3)
In Example 2, the plating resistance and developability were evaluated in the same manner except that the substrate was replaced with a copper-clad laminate (surface roughness 158 nm, surface contamination degree 2.5 mol%). The results are shown in Table 1.

(Comparative Example 4)
In Example 2, the plating resistance and developability were evaluated in the same manner except that the substrate was replaced with a copper clad laminate (surface roughness 204 nm, surface contamination level 5.2 mol%). The results are shown in Table 1.

(Comparative Example 5)
In Example 2, the plating resistance and developability were evaluated in the same manner except that the substrate was replaced with a copper-clad laminate (surface roughness 160 nm, surface contamination degree 3.7 mol%). The results are shown in Table 1.

(Comparative Example 6)
In Example 2, the developability was evaluated in the same manner except that the base material was replaced with a copper-clad laminate (surface roughness 535 nm, surface contamination degree 3.5 mol%). Spray development was performed for 40 seconds. Even if the test was carried out, the photosensitive layer remained as a residue on a part of the copper-clad laminate, and the plating resistance could not be evaluated. The results are shown in Table 1.

  From the results in Table 1, it was found that when a substrate having a surface roughness of 180 nm to 500 nm and a surface contamination degree of 4.0 mol% or less was used, the plating resistance and developability were good.

According to the method for producing a photosensitive laminate of the present invention, since plating resistance and developability are good and a high-definition pattern can be efficiently formed, a protective film, an interlayer insulating film, a solder resist pattern, etc. It can be suitably used for various pattern formation such as permanent pattern, color filter, pillar material, rib material, spacer, production of liquid crystal structural members such as partition walls, hologram, micromachine, proof, etc. It can be suitably used for forming.

Claims (8)

  A process comprising laminating a photosensitive layer made of a photosensitive composition on a substrate surface having a surface roughness of 180 nm to 500 nm and a surface contamination degree of 4.0 mol% or less. A manufacturing method of a layered product.   The method for producing a photosensitive laminate according to claim 1, wherein the photosensitive layer is formed by applying and drying the photosensitive composition on the surface of the substrate.   A photosensitive film in which a photosensitive layer is laminated on a temporary support is stacked so that the photosensitive layer is in contact with the surface of the substrate, and is subjected to at least one of heating and pressing, and the photosensitive layer is formed on the surface of the substrate. The manufacturing method of the photosensitive laminated body of Claim 1 which transfers and laminates.   The method for producing a photosensitive laminate according to any one of claims 1 to 3, wherein the base material is any one of a metal copper substrate and a substrate having at least one metal copper layer as at least one outermost layer.   The manufacturing method of the photosensitive laminated body in any one of Claim 1 to 4 with which a photosensitive composition contains a binder, a polymeric compound, a photoinitiator, and an inorganic filler at least.   A photosensitive laminate produced by the method according to claim 1. A laminate forming step of forming a photosensitive laminate by the method according to any one of claims 1 to 5,
An exposure step for pattern exposure on the photosensitive layer of the photosensitive laminate formed in the laminate formation step;
After the exposure step, a development step for removing unexposed areas in the photosensitive layer;
And a curing step of further curing the photosensitive layer after the development step.   A printed wiring board manufactured by the method according to claim 7.