JP2015018834A - Lamination method of resin layer and resin laminate for use therein - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lamination method of resin layer which allows for easy handling even for a resin layer of thin carrier film, while retarding entrainment of bubbles or creasing when laminating the resin layer, and to provide a resin laminate for use therein.SOLUTION: In a resin layer formation method for sticking a resin layer to an object of a manufacturing method of optical waveguide, the resin layer is formed on one surface of a carrier film, a resin laminate including a holding film on the surface of the carrier film opposite from the resin layer is used, and the resin layer surface of the resin laminate is stuck to the subject in the lamination method of resin layer. The resin laminate is used in the lamination method of resin layer.

Description

  The present invention relates to a method for laminating resin layers and a resin laminate used therefor.

In recent years, the development of the information society has been remarkable, and consumer devices such as personal computers, tablet terminals and mobile phones have been improved in performance and functionality. Industrial equipment includes wireless base stations, optical communication devices, servers and routers. There is a need for improved functionality in the same way, regardless of whether it is large or small, such as network-related equipment.
For this reason, flexible substrates such as semiconductor chip mounting substrates and mother boards are also being developed with higher density wiring and higher functionality.
Furthermore, development of an optical interconnection technique using an optical signal is being promoted from the viewpoints of electromagnetic radiation noise (EMI) from an electrical wiring board, resistance to radio wave contamination from the outside, and high speed and large capacity transmission. In particular, as an optical transmission path for using light for short-distance signal transmission between boards in a router or a server device, optical fibers that have a higher degree of freedom in wiring and can be densified than optical fibers. It is desirable to use a waveguide. Among them, an optical waveguide using a polymer material excellent in processability and economy is promising.

Generally, an electric wiring board is formed by forming an electric wiring made of metal on an insulating resin substrate and further forming a resin layer for protecting the electric wiring.
Such a method for forming electrical wiring includes a subtracting method in which wiring is formed by etching, and a relatively thin metal layer (seed layer) is formed on the surface of the insulating layer, and a dry film-like plating resist resin layer is formed thereon. A semi-additive method is used that can form a narrow pitch by forming a wiring to a required thickness by electroplating, removing the plating resist resin layer, and then removing the seed layer by soft etching.
In addition, a resin layer for protecting the electric wiring is formed on the outermost electric wiring, and a part of the resin layer is opened for electrical connection with various ICs and another electric wiring board. . As a method for producing such a resin layer, a method in which a dry film-like resin layer is laminated on an electric wiring by lamination and is formed into a resin layer patterned by photolithography is generally performed (patent) Reference 1).

  On the other hand, an optical waveguide is composed of a core pattern that propagates an optical signal embedded in a cladding layer, and a method of forming an optical waveguide by sequentially forming a lower cladding layer, a core pattern, and an upper cladding layer is generally performed. Yes. The core pattern can be formed by forming a core pattern forming resin layer on the lower clad layer, and patterning by exposure and development. In addition, there is an optical waveguide in which a cladding layer is patterned by exposure and development like the optical waveguide described in Patent Document 2 (see Patent Document 2). At this time, the cladding layer and the core pattern of the optical waveguide can also be formed by the same method as the resin layer forming method of the electric wiring board described above.

The above-described various resin layers in the form of a dry film are formed on a carrier film, and are once laminated on a subject (such as an electric wiring board or a clad layer) together with the carrier film. Thereafter, the resin layer is exposed through a photomask or the like. At this time, exposure through a carrier film is preferably used because there is little concern of contaminating the photomask. In addition, in the case of a resin layer in which a radical is generated by exposure and a pattern is formed by a radical reaction, the reaction is inhibited by oxygen in the air without the carrier film, and the pattern cannot be satisfactorily formed. There is also.
The high-resolution photosensitive resin is used for the plating resist resin layer used for forming the electric wiring and the resin layer for protecting the electric wiring, as the electric wiring becomes denser. In order to achieve the properties, the carrier film also needs to be highly transparent and thin.
In the case of the core pattern of the optical waveguide, the higher the transparency of the carrier film, the better the core pattern can be formed, and the light propagation loss becomes better. Also, the thinner the carrier film, the easier it is to obtain a pattern with a desired width.

JP 2004-319660 A JP 2005-326602 A

As described above, if the carrier film is thin, it is easy to form a pattern composed of a resin layer of a desired shape, but handling becomes difficult as the carrier film becomes thinner, and when the resin layer is pasted to the subject There are problems that air bubbles are easily involved and wrinkles are likely to occur. In addition, if the subject has unevenness, unevenness is likely to appear on the surface of the laminated resin, and there is a problem that it is difficult to control the thickness (to ensure the flatness of the resin).
The present invention has been made to solve the above-mentioned problems, and is easy to handle even when the carrier film is a thin resin layer. When the resin layer is laminated, the resin layer is less likely to cause entrainment of bubbles and wrinkles. It is an object to provide a method and a resin laminate used therefor.

As a result of intensive studies, the inventors have used a resin laminate in which a resin layer is formed on one surface of a carrier film and a holding film is provided on the surface opposite to the resin layer of the carrier film, It has been found that the above problem can be solved by bonding the resin layer surface of the resin laminate to the subject, and the present invention has been completed.
That is, the present invention provides the following (1) to (13).
(1) In a method of laminating a resin layer in which a resin layer is bonded to a subject,
Using the resin laminate in which the resin layer is formed on one surface of the carrier film and the holding film is provided on the surface opposite to the resin layer of the carrier film,
A method for laminating a resin layer, wherein the resin layer surface of the resin laminate is bonded to the subject;
(2) The method for laminating a resin layer according to (1), wherein the resin layer is a photosensitive resin layer,
(3) The method for laminating a resin layer according to claim 2, wherein after the resin layer is bonded, the holding film is peeled off and the resin layer is exposed.
(4) The method for laminating a resin layer according to (3), wherein after the photosensitive resin layer is exposed, the carrier film is peeled off and the resin layer is developed.
(5) The method for laminating a resin layer according to any one of (1) to (4), wherein the holding film is thicker than the carrier film.
(6) The method for laminating a resin layer according to any one of (1) to (5), wherein the resin layer is a resin layer containing a photoradical polymerizable compound or / and a photoradical polymerization initiator,
(7) The above (1) to (1), wherein the resin layer is at least one of a resist resin layer for electrical wiring formation, a resin layer for electrical wiring protection, and a lower cladding layer, a core layer, and an upper cladding layer of an optical waveguide. 6) A method for laminating a resin layer according to any one of
(8) The resin according to any one of (1) to (7), wherein the subject is an uneven subject, and the unevenness is embedded in the resin layer by bonding the resin layer to the subject. Layer stacking method,
(9) The method for laminating a resin layer according to any one of (1) to (8), wherein the bonding of the resin layer is performed by at least one of a roll laminator and a flat plate laminator.
(10) A resin laminate used in the method for laminating a resin layer according to any one of (1) to (9), wherein a resin layer is formed on one surface of a carrier film, and the carrier film A resin laminate comprising a holding film on the surface opposite to the resin layer.
(11) The resin laminate according to (10), wherein a cover film is provided on the surface of the resin layer opposite to the carrier film,
(12) The resin laminate according to (11), wherein at least one of the carrier film and the cover film is a film that shields actinic rays for sensitizing the resin layer,
(13) The resin laminate according to (11) or (12), wherein at least one of the carrier film, the cover film, and the holding film is a film that shields actinic rays for sensitizing the resin layer,

  According to the method for laminating a resin layer of the present invention, it is easy to handle even a resin layer with a thin carrier film, and it is possible to obtain a resin laminate that is less likely to cause entrainment of bubbles and wrinkles when laminating the resin layer. .

Hereinafter, the lamination method of the resin layer of this invention is demonstrated in detail.
The method for laminating a resin layer according to the present invention uses a resin laminate in which the resin layer is formed on one surface of a carrier film, and a holding film is provided on the surface opposite to the resin layer of the carrier film. This is a method of laminating a resin layer in which a resin layer surface of a body is bonded to the subject. By providing the holding film on the surface opposite to the resin layer forming surface of the carrier film, it is possible to impart toughness and appropriate rigidity to the carrier film, so there is an advantage that the handling property of the film with the resin layer is excellent. . In addition, since the resin layer surface is bonded to the subject while the holding film is provided, bubbles are not easily formed between the resin layer and the subject when the resin layer is bonded, and the carrier film is less likely to wrinkle.
The method for laminating the resin layer of the present invention is not limited to its use as long as it is a method of laminating a resin layer. The lower clad layer forming resin layer, the core layer forming resin layer, and the upper clad layer forming resin layer can be applied to a subject. The subject to which the resin layer is bonded is not particularly limited, but from the above viewpoint, the material for forming the electric wiring board, the electric wiring board in which the electric wiring is formed on the insulating resin layer, and the lower cladding layer of the optical waveguide And a core pattern. That is, as a specific example of the method for laminating the resin layers of the present invention, an electric wiring forming resist resin layer is bonded to the electric wiring board forming material, and an electric wiring protecting resin layer is bonded to the electric wiring board. The resin layer for forming the core layer and / or the resin layer for forming the upper cladding layer is bonded to the lower cladding layer of the optical waveguide. The resin layer for forming the upper cladding layer is bonded to the lower cladding layer and / or the core pattern of the optical waveguide. And bonding the resin layer for forming the lower clad layer of the optical waveguide to the electrical wiring board.

The resin layer used in the method for laminating a resin layer of the present invention is preferably a photosensitive resin layer. By using a photosensitive resin layer, when the resin layer is patterned by photolithography, etc., the holding film can be peeled off and exposed through a thin carrier film, thus forming a high-resolution and high-density pattern. It's easy to do. From the above viewpoint, the method for laminating the resin layers of the present invention may include a step of peeling the holding film and exposing the resin layer after the resin layers are bonded. The exposure method for patterning is not particularly limited, but for example, a method of irradiating an actinic ray in an image form through a negative mask pattern called artwork, direct activation without passing through a photomask using laser direct drawing For example, a method of irradiating an image with light rays.
In the method for laminating a resin layer according to the present invention, exposure of the resin layer through the carrier film is most preferable because the resin layer and the negative mask are not easily in direct contact with each other. You may expose by the method.
When peeling the holding film after pasting, from the viewpoint that peeling of only the holding film can be easily performed, the peeling strength between the holding film and the carrier film is weaker than the peeling strength between the resin layer and the carrier film, preferable.

  When the photosensitive resin layer is a negative type (resin layer in which the photosensitive part is cured) or a positive type (resin layer in which the photosensitive part can be developed) and is a resin layer that can be patterned using etching or the like. May have a step of peeling the carrier film after photosensitizing the resin layer and etching away the developable portion of the resin layer using various developing solutions. A resin layer having a desired shape can be obtained through the above steps.

  The method for laminating the resin layer is not particularly limited as long as it is a method for laminating a resin laminate composed of a holding film, a carrier film, and a resin layer to a subject, but a roll laminator, a flat plate laminator, and a flat plate press It is preferable that the number of bubbles and wrinkles at the time of bonding can be reduced. From the above viewpoint, it is more preferable that the bonding of the resin layer is performed by at least one of a roll laminator and a flat plate laminator. The temperature, pressure and the like may be appropriately adjusted by the above-described method, and further bonded under reduced pressure conditions.

Hereinafter, various members used in the method for laminating a resin layer of the present invention will be described in detail.
<Resin laminate>
The resin laminate used in the resin lamination method of the present invention is composed of a holding film, a carrier film, and a resin layer, and further includes a cover film on the surface opposite to the carrier film of the resin layer. Is preferred. By providing a holding film, the handling of the resin laminate is improved, and air bubbles are entrained in the interface between the subject and the resin layer due to bonding, and wrinkles of the carrier film are generated and transferred to the resin layer surface. Can suppress wrinkles.
Furthermore, if the subject has irregularities, it is possible to easily embed irregularities in the resin layer by pasting the resin laminate with the retaining film, compared to when there is no retaining film. There are few unevenness | corrugations on the resin surface, and substantially flatness can be ensured. If there are large irregularities on the surface of the resin layer, for example, there is a tendency that it is difficult to obtain a desired pattern width due to generation of a gap with the photomask due to the irregularities on the surface of the resin layer and refraction of exposure light when pattern exposure is performed. By using this method of laminating the resin layers, it becomes easy to form a desired pattern width. Specifically, a resin layer pattern when forming a resin layer for electrical wiring protection (irregularities are electrical wiring), or build-up formation of an optical waveguide on the electrical wiring board (lower clad with irregularities being electrical wiring or patterned) Misregistration such as meandering, partial thickening, and partial thinning of the wiring in the lower clad pattern and the core pattern during layering can be suppressed.

<Resin laminate with light-shielding film>
In the present invention, the resin laminate preferably has a light shielding film. The resin laminate having a light-shielding film is a resin laminate in which the carrier film and / or the cover film has a light-shielding property among the resin laminates composed of the carrier film, the resin layer, and the cover film. Of the resin laminates composed of four layers, a film, a carrier film, a resin layer, and a cover film, the holding film, the carrier film and / or the cover film is a resin laminate having light shielding properties. The light shielding property means a light shielding property against actinic rays capable of patterning the resin layer by exposure and development.
By providing a light-shielding film to at least one layer of the holding film, carrier film, and cover film, it is less susceptible to indoor and outdoor lighting including the same wavelength as the active light that can be patterned by the resin layer. Storing the resin layer is no longer necessary, such as the conventional packaging with a light-shielding film for shielding the wavelength and the use of a strict resin laminate storage and transfer form such as using illumination light with the same wavelength as the actinic ray. Also improves.
When the storage and transfer form is a form in which resin laminates on a sheet are stacked or in a roll form, even if only one surface of the resin layer is a light-shielding film, light can be shielded more efficiently. Become. From the above viewpoint, when the light-shielding film is used only on one surface in the case of a roll shape, it is better to externally wind the light-shielding film side.
In the present invention, it is sufficient that at least one layer of the holding film, the carrier film, and the cover film has a light-shielding property. However, the carrier film is a film that is transmissive to actinic rays, and the cover film has a light-shielding property. The above-described four-layered resin laminate is more preferable because it can be easily exposed through the carrier film during exposure of the resin layer, and the carrier film uses a transmissive film, and the holding film has a light shielding property. It is more preferable that the resin layered body has four layers since the resin layer can be shielded until just before exposure (step of peeling the holding film). At this time, the cover film may or may not have light shielding properties.

<Actinic ray>
The actinic ray for patterning the photosensitive resin layer used in the method for laminating a resin layer of the present invention is not particularly limited as long as the resin layer can be patterned, and ultraviolet rays, visible rays, infrared rays, those In particular, those using ultraviolet light are preferable. What is necessary is just to use the exposure amount suitable for the photosensitive resin layer as the exposure amount for patterning.

<Developing (etching) solution>
The developing (etching) solution for the resin layer used in the method for laminating the resin layer of the present invention is not particularly limited. When an organic solvent is used, the developing solution is not particularly limited as long as it can dissolve the resin composition for resin layer formation. For example, aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene, p-cymene; cyclic ethers such as tetrahydrofuran, 1,4-dioxane; methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, etc. Alcohol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and γ-butyrolactone; ethylene Carbonate, propylene car Carbonates such as nates; ethylene glycol monomethyl ether, ethylene glycol moethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether Polyhydric alcohol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoether Polyhydric alcohol alkyl ether acetates such as chill ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate; N, N-dimethylformamide, N , N-dimethylacetamide, amides such as N-methylpyrrolidone, and the like.
These organic solvents can be used alone or in combination of two or more.

When an alkaline solution is used for the developing (etching) solution, there is no particular limitation as long as it can dissolve a resin composition for forming a resin layer described later. For example, lithium hydroxide, sodium hydroxide, potassium hydroxide Alkali metal hydroxides such as lithium carbonate, sodium carbonate and potassium carbonate; Alkali metal bicarbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate; Potassium phosphate and sodium phosphate Alkali metal phosphates such as sodium pyrophosphate and potassium pyrophosphate; sodium salts such as sodium tetraborate and sodium metasilicate; ammonium salts such as ammonium carbonate and ammonium hydrogen carbonate; tetramethyl hydroxide Ammonium, triethanolamine, ethylenedia Emissions, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propanediol, solution or the like, such as an organic base such as 1,3-diamino-propanol-2-morpholine.
These bases of the alkaline developer can be used alone or in combination of two or more. What is necessary is just to adjust suitably the density | concentration of said base with the resin layer to be used.

  The development method is not particularly limited, and examples thereof include a spray method, a dip method, a paddle method, a spin method, a brushing method, and a scraping method. Moreover, you may use these image development methods together as needed.

<Holding film>
The holding film is not particularly limited as long as it is a film that can be peeled off from the carrier film. Examples thereof include polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefins such as polyethylene and polypropylene; polycarbonates, polyamides, polyimides, and polyamideimides. , Polyetherimide, polyether sulfide, polyether sulfone, polyether ketone, polyphenylene ether, polyphenylene sulfide, polyarylate, polysulfone, liquid crystal polymer and the like.
Among these, from the viewpoint of flexibility and toughness, it may be polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene, polycarbonate, polyamide, polyimide, polyamideimide, polyphenylene ether, polyphenylene sulfide, polyarylate, polysulfone. preferable.

  Among these, from the viewpoint of flexibility and toughness, it may be polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene, polycarbonate, polyamide, polyimide, polyamideimide, polyphenylene ether, polyphenylene sulfide, polyarylate, polysulfone. preferable.

The holding film may be provided with a peelable adhesive layer and may be a film with a re-peeling layer.
The thickness of the holding film may be appropriately changed as long as the carrier film can be held, but is preferably 10 to 500 μm. If it is 10 μm or more, the film strength is sufficient, and the carrier film can be provided with toughness and appropriate rigidity, and if it is 500 μm or less, sufficient flexibility can be obtained. From the above viewpoint, the thickness of the holding film is more preferably 10 to 300 μm, and particularly preferably 40 to 150 μm. Furthermore, it is preferable that the thickness of the holding film is thicker than the thickness of the carrier film. When the thickness of the holding film is thicker than the thickness of the carrier film, the handleability is further improved, and the flatness of the resin layer after bonding can be easily obtained.

  In the case of using a light-shielding holding film, a film in which a light-shielding layer is provided on the above film may be used, or a film of polyimide, polyamide, polyamideimide, or the like may be used. By using a holding film having a light-shielding property, it is difficult to be affected by indoor and outdoor illumination including the same wavelength as the active light that can be patterned on the resin layer, and storage of a strict resin laminate for shielding the wavelength or The form of transfer becomes unnecessary, and the storage stability of the resin layer is improved.

<Carrier film>
Although there is no restriction | limiting in particular as a carrier film, For example, Polyesters, such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; Polyolefins, such as polyethylene and a polypropylene; Polycarbonate, polyamide, polyimide, polyamideimide, polyetherimide, polyether sulfide, Examples include polyethersulfone, polyetherketone, polyphenylene ether, polyphenylene sulfide, polyarylate, polysulfone, and liquid crystal polymer.

  Among these, from the viewpoint of flexibility and toughness, it may be polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene, polycarbonate, polyamide, polyimide, polyamideimide, polyphenylene ether, polyphenylene sulfide, polyarylate, polysulfone. preferable.

Furthermore, it is more preferable to use a highly transparent type carrier film from the viewpoints of improving the transmittance of exposure actinic rays, reducing the pattern side wall roughness, and improving the pattern resolution. Examples of such highly transparent carrier films include Cosmo Shine A1517 and Cosmo Shine A4100 manufactured by Toyobo Co., Ltd.
In addition, you may use the film in which the mold release process was given by the silicone type compound, the fluorine-containing compound, etc. from a viewpoint of peelability improvement with a resin layer and a holding | maintenance film as needed.

  The thickness of the carrier film may be appropriately changed depending on the intended flexibility and resolution, but is preferably 1 to 75 μm. If it is 1 μm or more, the film strength is sufficient, and if it is 75 μm or less, sufficient flexibility can be obtained, and a pattern composed of a resin layer having a desired shape can be easily formed. From the above viewpoints, the thickness of the carrier film is more preferably 5 to 50 μm, and further preferably 7 to 25 μm from the viewpoint of ease of peeling of the carrier film and pattern resolution.

  In the case of using a light-shielding carrier film, a film in which a light-shielding layer is provided on the above film may be used, or a film of polyimide, polyamide, polyamideimide, or the like may be used. By using a light-shielding carrier film, the resin layer is less susceptible to indoor and outdoor lighting including the same wavelength as the actinic ray that can be patterned, and storage of a strict resin laminate for shielding the wavelength is possible. The form of transfer becomes unnecessary, and the storage stability of the resin layer is improved.

<Cover film>
Although there is no restriction | limiting in particular as a cover film, From a viewpoint of a softness | flexibility and toughness, For example, polyesters, such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate; Polyolefins, such as polyethylene and a polypropylene, etc. are mentioned suitably.

In addition, you may use the film in which the mold release process was given with the silicone type compound, the fluorine-containing compound, etc. from a viewpoint of peelability improvement with a resin layer as needed. The thickness of the cover film may be appropriately changed depending on the intended flexibility, but is preferably 10 to 250 μm. If it is 10 μm or more, the film strength is sufficient, and if it is 250 μm or less, sufficient flexibility is obtained. From the above viewpoint, the thickness of the cover film is more preferably 15 to 200 μm, and particularly preferably 20 to 150 μm.
In the case of using a light-shielding cover film, a film in which a light-shielding layer is provided on the above film or a film made of polyimide, polyamide, polyamideimide, or the like may be used. By using a cover film having a light shielding property, it is difficult to be affected by indoor and outdoor lighting including the same wavelength as the active light that can be patterned on the resin layer, and storage of a strict resin laminate for shielding the wavelength or The form of transfer becomes unnecessary, and the storage stability of the resin layer is improved.

<Resin layer>
The resin layer used in the method for laminating a resin layer of the present invention is not particularly limited as long as the resin layer can be bonded to a subject and the carrier film can be removed in the step after bonding, but a thermosetting resin layer or A photosensitive resin layer is preferable. In particular, the photosensitive resin layer is preferable because a high-resolution and high-density pattern can be formed by thinning the carrier film. From the above viewpoint, a negative photosensitive resin layer or a positive photosensitive resin layer is preferable.

  The method for forming the resin layer on one side of the carrier film is not particularly limited, but the resin composition for forming a resin layer is a resin varnish for forming a resin layer diluted with a suitable organic solvent, and spinned as necessary. Examples thereof include a coating method, a dip coating method, a spray method, a bar coating method, a roll coating method, a curtain coating method, a gravure coating method, a screen coating method, an ink jet coating method, and the like. Further, a drying process may be added after the application. Examples of the drying method include heat drying and reduced pressure drying. Moreover, you may use these together as needed. The step of applying may be performed after the holding film is laminated on the carrier film, or after the application, the holding film may be laminated on the carrier film.

  A cover film may be provided on the surface of the resin layer obtained above opposite to the carrier film. By providing a cover film, drying of the resin layer surface and adhesion of foreign substances etc. to the resin layer surface can be suppressed, and it is more preferable because it can be stored in a stacked state or stored in a roll shape. . What is necessary is just to peel a cover film before a bonding process.

The photosensitive resin layer-forming resin composition used in the method for laminating a resin layer of the present invention is particularly limited as long as it is a resin composition that can be patterned by photolithography after forming a resin layer on a carrier film. It is preferable that etching can be performed using various solvents, alkaline solutions, and the like. In the case of a negative resin layer, from the viewpoint of film formability, it is a resin composition containing at least (A) a polymer, (B) a polymerizable compound, and (C) a photopolymerization initiator from the viewpoint of photolithography processability. Good.
In the resin layer, (B) having a photoradical polymerizable compound as a polymerizable compound and / or (C) having a photoradical polymerization initiator as a photopolymerization initiator, having a carrier film on the resin layer at the time of exposure, Curing inhibition due to oxygen in the air can be effectively suppressed. From the above viewpoint, the component (B) is preferably a photoradical polymerizable compound, and the component (C) is preferably a photoradical polymerization initiator.

Hereinafter, the component (A) used in the present invention will be described.
The polymer (A) used in the present invention is for securing the strength when forming a resin laminate, and is not particularly limited as long as the object can be achieved. Examples thereof include resins, (meth) acrylic polymers, polycarbonates, polyarylates, polyether amides, polyether imides, polyether sulfones, and derivatives thereof. These polymers may be used alone or in combination of two or more.

When the resin layer developable with an alkaline solution is used, there is no particular limitation as long as the component (A) is an alkali-soluble polymer. For example, a carboxyl group-containing alkali represented by the following (1) to (6): Examples include soluble polymers.
(1) A carboxyl group-containing alkali-soluble polymer obtained by copolymerizing a compound having a carboxyl group and an ethylenically unsaturated group in the molecule with another compound having an ethylenically unsaturated group.

(2) Partially introducing an ethylenically unsaturated group into the side chain into a copolymer of a compound having a carboxyl group and an ethylenically unsaturated group in the molecule and another compound having an ethylenically unsaturated group A carboxyl group-containing alkali-soluble polymer obtained in this manner.

(3) A compound having a carboxyl group and an ethylenically unsaturated group in the molecule in a copolymer of a compound having an epoxy group and an ethylenically unsaturated group in the molecule and another compound having an ethylenically unsaturated group And a carboxyl group-containing alkali-soluble polymer obtained by reacting a polybasic acid anhydride with the generated hydroxyl group.

(4) A compound having an hydroxyl group and an ethylenically unsaturated group in the molecule is reacted with a copolymer of an acid anhydride having an ethylenically unsaturated group and another compound having an ethylenically unsaturated group. Obtained carboxyl group-containing alkali-soluble polymer.

(5) A carboxyl group-containing alkali-soluble polymer obtained by reacting a polybasic acid anhydride with a polyaddition product of a bifunctional epoxy resin and a dicarboxylic acid or a bifunctional phenol compound.

(6) A carboxyl group-containing alkali-soluble polymer obtained by reacting a polybasic acid anhydride with a hydroxyl group of a polyaddition product of a bifunctional oxetane compound and a dicarboxylic acid or a bifunctional phenol compound.

Among these, a carboxyl group-containing alkali-soluble polymer represented by the above (1) to (4) is preferable from the viewpoint of transparency and solubility in an alkaline developer.
These polymers are preferably (meth) acrylic polymers having a (meth) acryloyl group. Here, the (meth) acryloyl group is an acryloyl group and / or methacryloyl group, and the (meth) acrylic polymer is a monomer of acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, and derivatives thereof. And a polymer obtained by polymerizing this.
The (meth) acrylic polymer is a copolymer obtained by polymerizing two or more of the above-described monomers, and further, the above-described monomers and, if necessary, (meta ) A copolymer containing a monomer other than the above having an ethylenically unsaturated group other than an acryloyl group may be used. Further, it may be a mixture of a plurality of (meth) acrylic polymers.

The weight average molecular weight of the carboxyl group-containing alkali-soluble polymer is preferably 1,000 to 3,000,000, more preferably 3,000 to 2,000,000, and 5,000 to 1,000. Is more preferable. If it is 1,000 or more, the molecular weight is large, so the strength of the cured product is sufficient when it is a resin composition, and if it is 3,000,000 or less, solubility in an alkaline developer and (B) polymerizability. Good compatibility with compounds.
The weight average molecular weight in the present invention is a value measured by gel permeation chromatography (GPC) and converted to standard polystyrene.

In the step of forming a pattern by development, the carboxyl group-containing alkali-soluble polymer preferably has an acid value so that it can be developed with an alkaline developer. For example, when an alkaline developer is used, the acid value is preferably 20 to 300 mgKOH / g.
If the acid value is 20 mgKOH / g or more, development is easy, and if it is 300 mgKOH / g or less, the developer resistance does not deteriorate. From the above viewpoint, the acid value is more preferably 30 to 250 mgKOH / g, and particularly preferably 40 to 200 mgKOH / g.
The developer resistance refers to a property that a resist film that is not removed by development and becomes a pattern is not attacked by the developer.

  When an alkaline quasi-aqueous developer composed of an alkaline aqueous solution and one or more organic solvents is used as the alkaline developer, the acid value is preferably 10 to 260 mgKOH / g. If the acid value is 10 mgKOH / g or more, development is easy, and if it is 260 mgKOH / g or less, the developer resistance is not lowered. From the above viewpoint, the acid value is more preferably 20 to 250 mgKOH / g, and particularly preferably 30 to 200 mgKOH / g.

  It is preferable that the compounding quantity of (A) component is 10-85 mass% with respect to the total amount of (A) component and (B) component. If it is 10% by mass or more, the strength and flexibility of the cured product of the resin composition are sufficient, and if it is 85% by mass or less, it is easily entangled by the component (B) during exposure, and is resistant to development. There is no shortage of liquidity. From the above viewpoint, the blending amount of the component (A) is more preferably 20 to 80% by mass, and particularly preferably 25 to 75% by mass.

Hereinafter, the component (B) used in the present invention will be described.
There is no restriction | limiting in particular as a polymeric compound of (B) component, For example, the compound which has polymeric substituents, such as an ethylenically unsaturated group, the compound which has two or more epoxy groups in a molecule | numerator etc. are mentioned suitably. .

  Specific examples include (meth) acrylate, vinylidene halide, vinyl ether, vinyl ester, vinyl pyridine, vinyl amide, arylated vinyl and the like. As the (meth) acrylate, any of monofunctional, bifunctional, or polyfunctional ones can be used.

  There is no restriction | limiting in particular as monofunctional (meth) acrylate, For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) Acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, butoxyethyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate , Octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetra Sil (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3- Aliphatic (meth) acrylates such as chloro-2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate; cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, di Cyclopentenyl (meth) acrylate, cycloaliphatic (meth) acrylate such as isobornyl (meth) acrylate; phenyl (meth) acrylate, nonylphenyl (meth) acrylate, p-kumi Phenyl (meth) acrylate, o-biphenyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2 -Hydroxy-3- (o-phenylphenoxy) propyl (meth) acrylate, 2-hydroxy-3- (1-naphthoxy) propyl (meth) acrylate, 2-hydroxy-3- (2-naphthoxy) propyl (meth) acrylate Aromatic (meth) acrylates such as 2-tetrahydrofurfuryl (meth) acrylate, N- (meth) acryloyloxyethylhexahydrophthalimide, 2- (meth) acryloyloxyethyl-N-carbazole and other heterocyclic (meth Acrylate These ethoxylated products; these propoxylated products; these ethoxylated propoxylated products; these caprolactone-modified products and the like.

There is no restriction | limiting in particular as bifunctional (meth) acrylate, For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 2-methyl-1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-butyl-2-ethyl-1, 3-propanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, glycerin di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate Aliphatic (meth) acrylates such as: cyclohexanedimethanol (meth) acrylate, ethoxylated cyclohexanedimethanol (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate, hydrogenated bisphenol F Alicyclic (meth) acrylates such as meth) acrylate; aromatics such as bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, bisphenol AF di (meth) acrylate, and fluorene type di (meth) acrylate Heterocyclic (meth) acrylates such as isocyanuric acid di (meth) acrylate; ethoxylated products thereof; propoxylated products thereof; ethoxylated propoxylated products thereof; modified caprolactone products thereof; neopentyl glycol type Aliphatic epoxy (meth) acrylates such as epoxy (meth) acrylate; cyclohexanedimethanol type epoxy (meth) acrylate, hydrogenated bisphenol A type epoxy (meth) acrylate, hydrogenated bisphenol F type epoxy (meth) Alicyclic epoxy (meth) acrylates such as acrylate; resorcinol type epoxy (meth) acrylate, bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, bisphenol AF type epoxy (meth) acrylate, fluorene type epoxy Aromatic epoxy (meth) acrylates such as (meth) acrylates may be mentioned.
Among these, from the viewpoint of transparency and heat resistance, the above alicyclic (meth) acrylates; the above aromatic (meth) acrylates; the above heterocyclic (meth) acrylates; these ethoxylated products; and these propoxylated products. These ethoxylated propoxy compounds; these caprolactone-modified products; the alicyclic epoxy (meth) acrylates; and the aromatic epoxy (meth) acrylates.

  The trifunctional or higher polyfunctional (meth) acrylate is not particularly limited. For example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra ( Aliphatic (meth) acrylates such as (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; heterocyclic (meth) acrylates such as isocyanuric acid tri (meth) acrylate; these ethoxys These propoxylated products; These ethoxylated propoxylated products; These caprolactone modified products; Phenol novolac epoxy (meth) acrylate, Cresol novolac epoxy ( Aromatic epoxy (meth) acrylates such as data) acrylate.

  The above-mentioned monofunctional (meth) acrylate, bifunctional (meth) acrylate, and trifunctional or higher polyfunctional (meth) acrylate can be used alone or in combination of two or more. In addition, (meth) acrylates having different numbers of functional groups can be used in combination. Furthermore, it can also be used in combination with other polymerizable compounds.

(B) The polymeric compound may contain urethane (meth) acrylate further as needed. By blending urethane (meth) acrylate, flexibility or toughness derived from urethane bonds can be imparted to the cured product.
There is no restriction | limiting in particular as urethane (meth) acrylate, For example, the urethane (meth) acrylate represented by following (I)-(IV) is mentioned.
(I) Urethane (meth) acrylate obtained by reacting a bifunctional alcohol compound, a bifunctional isocyanate compound, and a (meth) acrylate having a hydroxyl group.
(II) Urethane (meth) acrylate obtained by reacting a bifunctional alcohol compound, a bifunctional isocyanate compound, and a (meth) acrylate having an isocyanate group.
(III) Urethane (meth) acrylate obtained by reacting a polyfunctional isocyanate compound with (meth) acrylate having a hydroxyl group.
(IV) Urethane (meth) acrylate obtained by reacting a polyfunctional alcohol compound with (meth) acrylate having an isocyanate group.

  Moreover, what contains the compound which has a 2 or more epoxy group in a molecule | numerator as a preferable (B) polymeric compound other than the said (meth) acrylate is mentioned.

Specifically, hydroquinone type epoxy resin, resorcinol type epoxy resin, catechol type epoxy resin, bisphenol A type epoxy resin, tetrabromobisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, bisphenol AD type epoxy Resin, biphenyl type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, etc. bifunctional phenol glycidyl ether type epoxy resin; hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, hydrogenated 2,2′- Hydrogenated bifunctional phenol glycidyl ether type epoxy resin such as biphenol type epoxy resin, hydrogenated 4,4′-biphenol type epoxy resin; phenol novolac type epoxy resin, cresol novo Polyfunctional phenol glycidyl ether type epoxy resin having three or more functional groups such as epoxy type epoxy resin, dicyclopentadiene-phenol type epoxy resin, dicyclopentadiene-cresol type epoxy resin, tetraphenylolethane type epoxy resin; polyethylene glycol type epoxy Resin, polypropylene glycol type epoxy resin, neopentyl glycol type epoxy resin, bifunctional aliphatic alcohol glycidyl ether type epoxy resin such as 1,6-hexanediol type epoxy resin; cyclohexanediol type epoxy resin, cyclohexanedimethanol type epoxy resin, Bifunctional alicyclic alcohol glycidyl ether type epoxy resin such as tricyclodecane dimethanol type epoxy resin; Trimethylolpropane type epoxy resin, sorbi Trifunctional or higher functional aliphatic alcohol glycidyl ether type epoxy resin such as tall type epoxy resin and glycerin type epoxy resin; bifunctional aromatic glycidyl ester such as diglycidyl phthalate; tetrahydrophthalic acid diglycidyl ester, hexahydrophthal Bifunctional alicyclic glycidyl esters such as acid diglycidyl esters; Bifunctional aromatic glycidyl amines such as N, N-diglycidylaniline and N, N-diglycidyltrifluoromethylaniline; N, N, N ′, N ′ -Trifunctional or more polyfunctional aromatics such as tetraglycidyl-4,4-diaminodiphenylmethane, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, N, N, o-triglycidyl-p-aminophenol Glycidylamine; Alicyclic die Bifunctional alicyclic epoxy resins such as xiacetal, alicyclic diepoxy adipate, alicyclic diepoxycarboxylate, vinylcyclohexene dioxide; 1,2-bis (hydroxymethyl) -1-butanol 1,2- Trifunctional or higher polyfunctional alicyclic epoxy resin such as epoxy-4- (2-oxiranyl) cyclohexane adduct; Trifunctional or higher functional heterocyclic epoxy resin such as triglycidyl isocyanurate; Organopolysiloxane type epoxy resin And silicon-containing bifunctional or trifunctional or higher polyfunctional epoxy resins.
These compounds can be used alone or in combination of two or more, and can also be used in combination with other polymerizable compounds.

  It is preferable that the compounding quantity of the polymeric compound of (B) component is 15-90 mass% with respect to the total amount of (A) component and (B) component. If it is 15% by mass or more, it is easy to entangle the polymer of the component (A) and harden the developer resistance, and if it is 90% by mass or less, the film strength of the cured film and Flexibility is sufficient. From the above viewpoint, the blending amount of the component (B) is more preferably 20 to 80% by mass, and particularly preferably 25 to 75% by mass.

Hereinafter, the component (C) used in the present invention will be described.
The photopolymerization initiator of component (C) is not particularly limited as long as the polymerization is initiated by irradiation with actinic rays such as ultraviolet rays. For example, an ethylenically unsaturated group is used as the polymerizable compound of component (B). When using the compound which has, radical photopolymerization initiator etc. are mentioned.

There is no restriction | limiting in particular as radical photopolymerization initiator, For example, benzoinketals, such as 2, 2- dimethoxy- 1, 2- diphenyl ethane- 1-one; 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl -1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4 [4 Α-hydroxy ketones such as-(2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one; methyl phenylglyoxylate, ethyl phenylglyoxylate, 2- (2-hydroxyoxyphenylacetate) Ethoxy) ethyl, oxyphenylacetic acid 2- (2-oxo-2-phenylacetoxyate) G) Glyoxyesters such as ethyl; 2-benzyl-2-dimethylamino-1- (4-morpholin-4-ylphenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) ) -1- (4-Morpholin-4-ylphenyl) -butan-1-one, 1,2-methyl-1- [4- (methylthio) phenyl]-(4-morpholin) -2-ylpropane Α-amino ketones such as -1-one; 1,2-octanedione, 1- [4- (phenylthio), 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2- Oxime esters such as methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime); bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis Phosphine oxides such as 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 2- (o-chlorophenyl) -4,5-diphenylimidazole 2-mer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxy) 2,4,5-triarylimidazole dimers such as phenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer; benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone, N, N′-tetraethyl-4,4 ′ Benzophenone compounds such as diaminobenzophenone and 4-methoxy-4′-dimethylaminobenzophenone; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2, Quinone compounds such as 3-dimethylanthraquinone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin, methyl benzoin and ethylben Benzoin compounds such as indium; benzyl compounds such as benzyldimethyl ketal; acridine compounds such as 9-phenylacridine and 1,7-bis (9,9′-acridinylheptane): N-phenylglycine, coumarin and the like .
In the 2,4,5-triarylimidazole dimer, the substituents of the aryl groups at the two triarylimidazole sites may give the same and symmetric compounds, but give differently asymmetric compounds. May be.
The above radical photopolymerization initiators can be used alone or in combination of two or more. Furthermore, it can also be used in combination with an appropriate sensitizer.

  Moreover, when using an epoxy resin as a polymeric compound of (B) component, a photocationic polymerization initiator etc. are mentioned as a photoinitiator of (C) component.

  Examples of the photocationic polymerization initiator include aryl diazonium salts such as p-methoxybenzenediazonium hexafluorophosphate, diaryliodonium salts such as diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate; triphenylsulfonium hexafluorophosphate, triphenylsulfonium Triarylsulfonium salts such as hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium pentafluorohydroxyantimonate; Triphenylselenonium hexa Triarylselenonium salts such as fluorophosphate, triphenylselenonium tetrafluoroborate, triphenylselenonium hexafluoroantimonate; dialkylphenacyl such as dimethylphenacylsulfonium hexafluoroantimonate, diethylphenacylsulfonium hexafluoroantimonate Sulfonium salts; dialkyl-4-hydroxy salts such as 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate and 4-hydroxyphenylbenzylmethylsulfonium hexafluoroantimonate; α-hydroxymethylbenzoin sulfonate, N-hydroxyimide sulfonate, α -Sulphonic acid esters such as sulfonyloxyketone and β-sulfoniloxyketone.

  These photocationic polymerization initiators can be used alone or in combination of two or more. Furthermore, it can also be used in combination with an appropriate sensitizer.

  (C) It is preferable that the compounding quantity of the polymerization initiator of a component is 0.1-10 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component. If it is 0.1 parts by mass or more, curing is sufficient, and if it is 10 parts by mass or less, a sufficient degree of curing is obtained. From the above viewpoint, the amount of component (C) is more preferably 0.3 to 7 parts by mass, and particularly preferably 0.5 to 5 parts by mass.

Moreover, it is preferable to mix | blend a thermosetting component from the viewpoint of accelerating | stimulating hardening by a thermosetting process in the photosensitive resin layer forming resin composition.
Examples of the thermosetting component include compounds having one or more epoxy groups in the molecule, polyfunctional blocked isocyanates such as an isocyanurate type trimer of hexamethylene diisocyanate, and the like.
The blending amount of the thermosetting component is preferably 0.1 to 30 parts by mass, more preferably 1 to 25 parts by mass, and still more preferably 3 to 100 parts by mass of the total amount of the component (A) and the component (B). 20 parts by mass.

In the resin composition for forming a resin layer used in the present invention, an antioxidant, an anti-yellowing agent, an ultraviolet absorber, a visible light absorber, a colorant, a plasticizer, a stabilizer, and a filler are included as necessary. So-called additives such as may be added.
The resin composition for forming a resin layer used in the present invention may be diluted with a suitable organic solvent and used as a resin varnish. The organic solvent used here is not particularly limited as long as it can dissolve the resin composition. For example, aromatic hydrocarbons such as toluene, xylene, mesitylene, cumene, p-cymene; tetrahydrofuran, 1, 4 -Cyclic ethers such as dioxane; alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; acetic acid Esters such as methyl, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate and γ-butyrolactone; carbonates such as ethylene carbonate and propylene carbonate; ethylene glycol monomethyl ether, ethylene glycol moet Ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol Polyhydric alcohol alkyl ethers such as dimethyl ether and diethylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol Polyhydric alcohol alkyl ether acetates such as coal monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate; N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc. And amides.
These organic solvents can be used alone or in combination of two or more. Moreover, it is preferable that the solid content density | concentration in a resin varnish is 20-80 mass% normally.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded.
In addition, the weight average molecular weight and acid value of the (meth) acrylic polymer (A) which is the base polymer of the resin composition for forming a resin layer used in the clad layer forming resin laminate were measured by the following methods.
(1) Weight average molecular weight It measured using the gel permeation chromatography (GPC) (The Tosoh Co., Ltd. product name "SD-8022", "DP-8020", and "RI-8020"). In addition, the Hitachi Chemical Co., Ltd. product name "Gelpack GL-A150-S" and "Gelpack GL-A160-S" were used for the column.
(2) Acid value 0.1 mol / L potassium hydroxide aqueous solution was dripped at the obtained polymer solution, and it computed from the amount of potassium hydroxide aqueous solution required for neutralization. At this time, the point at which the phenolphthalein added as an indicator changed color from colorless to pink was defined as the neutralization point.

Example 1
[Preparation of resin laminate for forming clad layer]
(1) Preparation of base polymer; (meth) acrylic polymer (A) In a flask equipped with a stirrer, a cooling tube, a gas introduction tube, a dropping funnel, and a thermometer, 46 parts by mass of propylene glycol monomethyl ether acetate and methyl lactate 23 parts by mass was weighed and stirred while introducing nitrogen gas. The liquid temperature was raised to 65 ° C., 47 parts by weight of methyl methacrylate, 33 parts by weight of butyl acrylate, 16 parts by weight of 2-hydroxyethyl methacrylate, 14 parts by weight of methacrylic acid, 2,2′-azobis (2,4-dimethylvaleronitrile ) A mixture of 3 parts by mass, 46 parts by mass of propylene glycol monomethyl ether acetate and 23 parts by mass of methyl lactate was added dropwise over 3 hours, followed by stirring at 65 ° C. for 3 hours, and further stirring at 95 ° C. for 1 hour. A (meth) acrylic polymer (A) solution (solid content: 45% by mass) was obtained.
The obtained (meth) acrylic polymer (A) had a weight average molecular weight (in terms of standard polystyrene) of 3.9 × 10 ⁴ and an acid value of 79 mgKOH / g.

(2) Preparation of Cladding Layer Forming Resin Varnish (A) As a polymer, the above (meth) acrylic polymer (A) solution (solid content 45 mass%) 84 mass parts (solid content 38 mass parts), (B) Polymerizability As compounds, urethane (meth) acrylate having a polyester skeleton (made by Shin-Nakamura Chemical Co., Ltd., trade name “U-200AX”) 33 parts by mass, and urethane (meth) acrylate having a polypropylene glycol skeleton (Shin-Nakamura Chemical Co., Ltd.) Co., Ltd., trade name “UA-4200”) 15 parts by mass, polyfunctional block isocyanate solution obtained by protecting isocyanurate type trimer of hexamethylene diisocyanate with methyl ethyl ketone oxime as a thermosetting component (solid content: 75% by mass) (Sumika Bayer Urethane Co., Ltd., trade name “Sumijour BL3175”) 20 parts by mass (Solid content 15 parts by mass), (C) As a photopolymerization initiator, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one (BASF Japan ( Co., Ltd., trade name “Irgacure 2959”) 1 part by mass, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (BASF Japan Ltd., trade name “Irgacure 819”) 1 part by mass, and dilution As an organic solvent, 23 parts by mass of propylene glycol monomethyl ether acetate was mixed with stirring to obtain a mixture. Then, the mixture was subjected to pressure filtration using a polyflon filter having a pore diameter of 2 μm (trade name “PF020” manufactured by Advantech Toyo Co., Ltd.) and then degassed under reduced pressure to obtain a resin varnish for forming a cladding layer.

(3) Production of carrier film with holding film One surface (release treatment surface) of polyethylene terephthalate (PET) film (trade name: Cosmo Shine A1517, manufactured by Toyobo Co., Ltd., thickness: 16 μm) as a carrier film In addition, a relaminating layer surface of a PET film with a re-peeling layer (trade name: Panaprotect ET-50KB, manufactured by Panac Co., Ltd., thickness 57 μm), which is a holding film, is a roll laminator (manufactured by Hitachi Chemical Technoplant Co., Ltd., HLM). -1500), lamination was performed under conditions of a pressure of 0.4 MPa, a temperature of 30 ° C., and a laminating speed of 1.0 m / min.

(4) Production of Cladding Layer Forming Resin Laminate The above obtained clad layer forming resin varnish is a PET film (trade name: Cosmo Shine A1517, Toyobo Co., Ltd.) with a 57 μm thick holding film. Coated on a non-treated surface (opposite surface of holding film) manufactured by Co., Ltd. using a coating machine (product name “Multicoater TM-MC” manufactured by Hirano Techseed Co., Ltd.), and 100 ° C. After drying for 20 minutes, a surface release treated PET film (“Purex A31” manufactured by Teijin DuPont Films, Inc., thickness 25 μm) was applied as a cover film to obtain a clad layer forming resin laminate.
The thickness of the resin layer (cladding layer) formed from the electrical wiring protecting resin layer and the cladding layer forming resin layer can be arbitrarily adjusted by adjusting the gap of the coating machine. Moreover, the film thickness of the clad layer after coating on the PET film was the same as the film thickness after curing. In addition, about the film thickness of the resin layer for clad layer formation used in the below-mentioned Example, it describes in each Example. The film thickness of the clad layer forming resin layer described in the examples is the film thickness after coating.

Example 2
[Preparation of core layer-forming resin laminate]
(A) As a polymer, 26 parts by mass of a phenoxy resin (trade name: Phenototo YP-70, manufactured by Toto Kasei Co., Ltd.), (B) 9,9-bis [4- (2-acryloyloxy) as a polymerizable compound Ethoxy) phenyl] fluorene (trade name: A-BPEF, manufactured by Shin-Nakamura Chemical Co., Ltd.) 36 parts by mass, and bisphenol A type epoxy acrylate (trade name: EA-1020, manufactured by Shin-Nakamura Chemical Co., Ltd.) 36 (C) As a photopolymerization initiator, 1 part by mass of bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (trade name: Irgacure 819, manufactured by BASF Japan Ltd.) and 1- [4 -(2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one (trade name: Irgacure 2959, BASF Yapan Ltd.) 1 part by weight, except for using 40 parts by mass of propylene glycol monomethyl ether acetate as an organic solvent was prepared resin varnish for forming a core layer by the same method and conditions as in Example 1. Thereafter, pressure filtration and degassing under reduced pressure were performed under the same method and conditions as in Example 1 above.
The resin varnish for forming a core layer obtained above is a PET film (trade name: Cosmo Shine A1517, manufactured by Toyobo Co., Ltd., thickness) which is a carrier film with a holding film having a thickness of 57 μm described in Example 1. : 16 μm) on the non-treated surface and dried by the same method as in Example 1 above, and then a release PET film (trade name: Purex A31, Teijin DuPont Films, Inc., thickness: 25 μm as a cover film) ) Was attached so that the release surface was on the resin side, to obtain a core layer-forming resin laminate. At this time, the thickness of the resin layer can be arbitrarily adjusted by adjusting the gap of the coating machine. In this example, the thickness of the core layer-forming resin laminate used was 50 μm. The film thickness of the core layer forming resin laminate described in the examples is the film thickness after coating.

Example 3
[Production of electrical wiring board]
<Formation of electrical wiring>
100 mm x 100 mm single-sided copper foil polyimide film (manufactured by Nippon Steel & Sumikin Co., Ltd., trade name: MC12-25-00CEM (copper foil is manufactured by Furukawa Electric Co., Ltd., trade name: F2-WS) as a substrate with metal foil Photosensitive dry film (made by Hitachi Chemical Co., Ltd., product name: Photec, thickness: 25 μm) with a cover film peeled off from a copper foil surface of 12 mm thick, roll laminator (manufactured by Hitachi Chemical Technoplant Co., Ltd.) , HLM-1500) was laminated under conditions of a pressure of 0.4 MPa, a temperature of 110 ° C., and a laminating speed of 1.0 m / min. Thereafter, using an ultraviolet exposure machine (EXM-1172, manufactured by Oak Manufacturing Co., Ltd.), 350 mJ of ultraviolet rays (wavelength 365 nm) is passed through a negative photomask having openings (30 mm × 150 μm × 5 locations, 250 μm intervals). Irradiated at / cm ² . Thereafter, the support film of the dry film was peeled off, the uncured dry film was developed and removed using a developer (1% by mass aqueous sodium carbonate solution), and then the copper foil was etched with an aqueous ferric chloride solution. Furthermore, the hardened dry film was peeled and removed with a stripping solution (3 mass% sodium hydroxide aqueous solution) to form an electrical wiring.

<Formation of resin layer for electrical wiring protection>
The 25 μm-thick clad layer-forming resin laminate obtained in Example 1 was used as an electrical wiring protecting resin laminate. First, after peeling the cover film of the resin laminate for electrical wiring protection, using a vacuum pressure type flat plate laminator (manufactured by Meiki Seisakusho, MVLP-500), vacuuming to 500 Pa or less, pressure 0.4 MPa, Lamination was performed by thermocompression bonding under conditions of a temperature of 110 ° C. and a pressing time of 30 seconds. Subsequently, the re-peeled layer-attached PET film, which is a holding film for the electrical wiring protecting resin laminate, was peeled off. Bubble entrainment and wrinkling of the carrier film did not occur.
Next, using an ultraviolet exposure machine (EXM-1172, manufactured by Oak Manufacturing Co., Ltd.), both ends of the electric wiring 500 μm outside the opening through a negative photomask having an opening (29 mm × 90 mm). Was irradiated with ultraviolet rays (wavelength 365 nm) at 350 mJ / cm ² from the carrier film side of the resin layer for electrical wiring protection. Thereafter, the carrier film was peeled off, developed using a 1% by mass aqueous potassium carbonate solution as an alkaline developer, and further washed with pure water for 30 seconds. Subsequently, it dried at 100 degreeC for 5 minutes. Further, 3.0 J / cm ^{2 was} irradiated from the surface on which the resin layer for electrical wiring protection was formed using the above-mentioned UV exposure machine, photocured, and then heated at 170 ° C. for 1 hour to thermally cure the resin layer.
The unevenness of the obtained resin layer for electrical wiring protection was within ± 2 μm. The width of the resin layer for electrical wiring protection was also a predetermined length and was good.

Example 4
[Fabrication of optical waveguide]
<Formation of lower cladding layer>
A 25 μm-thick clad layer-forming resin laminate is laminated in the same manner as in Example 3 so as to cover the electrical wiring obtained in Example 3, and then the ladder layer-forming resin laminate is peeled off. Then, a lower clad layer (90 mm × 90 mm) was formed. Bubble entrainment and wrinkling of the carrier film did not occur.

<Formation of core layer>
Next, after the cover film was peeled off the 50 μm-thick core layer-forming resin laminate obtained in Example 2 from the lower clad layer forming surface side formed above, a roll laminator (Hitachi Chemical Technoplant Co., Ltd.) Manufactured by HLM-1500) under the conditions of a pressure of 0.4 MPa, a temperature of 50 ° C., and a laminating speed of 0.2 m / min. Next, after vacuuming to 500 Pa or less using the above-described vacuum pressurization type plate laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.), conditions of pressure 0.4 MPa, temperature 70 ° C., pressurization time 30 seconds And thermocompression bonded. Next, the holding film was peeled off to form a core layer. Bubble entrainment and wrinkling of the carrier film did not occur.

<Formation of core pattern>
Subsequently, a negative photomask having openings (45 μm × 80 mm) provided at eight positions at a pitch of 250 μm is passed through the negative photomask so that the openings cross the electric wiring on the lower cladding layer. Using the above-mentioned ultraviolet exposure machine from the film side, ultraviolet rays (wavelength 365 nm) were irradiated at 0.8 J / cm ² and heated after exposure at 80 ° C. for 5 minutes. Thereafter, the PET film as the carrier film was peeled off and etched using a developer (propylene glycol monomethyl ether acetate / N, N-dimethylacetamide = 8/2, mass ratio). Then, it wash | cleaned using the washing | cleaning liquid (isopropanol), and heat-dried at 100 degreeC for 10 minute (s), and formed the core pattern.

<Formation of upper clad layer>
After peeling the cover film of the 75 μm-thick clad layer-forming resin laminate obtained in Example 1, a vacuum pressure type flat plate laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd.) was used to make a vacuum at 500 Pa or less. After drawing, the film was laminated by thermocompression bonding under conditions of a pressure of 0.4 MPa, a temperature of 110 ° C., and a pressing time of 30 seconds. Next, the holding film was peeled off. Bubble entrainment and wrinkling of the carrier film did not occur.
Subsequently, the position of the center of the opening and the center of the substrate are aligned through a negative photomask having an opening (90 mm × 90 mm) using an ultraviolet exposure machine (EXM-1172, manufactured by Oak Manufacturing Co., Ltd.). Then, ultraviolet rays (wavelength 365 nm) were irradiated at 350 mJ / cm ² from the carrier film side of the clad layer forming resin laminate. Thereafter, the carrier film was peeled off, developed using a developer (1% by mass potassium carbonate aqueous solution), and further washed with pure water for 30 seconds.
The unevenness of the obtained core layer was within ± 0.5 μm, and the unevenness of the upper cladding layer was within ± 3 μm.

Comparative Example 1
In Example 1, a clad layer-forming resin laminate without using a holding film (used as a resin layer for electrical wiring protection) was formed. In Example 3, the resin layer for electrical wiring protection was formed in the same manner except that the clad layer forming resin laminate obtained without using the holding film obtained above was laminated as a resin layer for electrical wiring protection. Bubbles were generated between the resin layer and the electric wiring board after lamination, and wrinkles were generated on the carrier film. The outline of the resin layer meandered by ± 4 μm and was not a good shape.

Comparative Example 2
In Example 2, a core layer-forming resin laminate without using a holding film was formed. In Example 4, an optical waveguide was formed in the same manner except that the core pattern was formed using the core layer-forming resin laminate without using the holding film obtained above. After laminating the core layer-forming resin laminate, bubbles were generated between the lower clad layer and the core layer, and wrinkles were generated in the carrier film. The unevenness of the obtained core layer was ± 1.0 μm.

Comparative Example 3
In Example 1, a clad layer forming resin laminate without using a holding film was formed. In Example 4, an optical waveguide was formed in the same manner except that the upper clad layer was formed using the clad layer forming resin laminate not using the holding film obtained above. After laminating the clad layer forming resin laminate, bubbles were generated between the lower clad layer and the upper clad layer, and wrinkles were generated in the carrier film. The unevenness of the obtained core layer was ± 4.5 μm.

Example 5
In Example 1, the cover film of the clad layer forming resin laminate is a 25 μm polyimide film (polyimide; Upilex RN (manufactured by Ube Nitto Kasei Co., Ltd.)), and the resin laminate is in a roll shape with the cover film side facing outside. Formed. I left it under sunlight for 1 hour. Then, when the resin layer for electrical wiring protection was formed like Example 3 except having used the resin laminated body obtained above, the pattern of the resin layer was able to be formed favorably.

Example 6
In Example 1, a resin laminate was formed in a roll shape with the cover film side facing outside without using a holding film. I left it under sunlight for 1 hour. Thereafter, the holding film used in Example 1 was rolled laminator (manufactured by Hitachi Chemical Technoplant Co., Ltd., HLM-1500) under the conditions of pressure 0.4 MPa, temperature 30 ° C., laminating speed 0.2 m / min. When the resin laminate was laminated on the carrier film of the resin laminate obtained in the same manner as in Example 3 and a resin layer for electrical wiring protection was formed, a resin layer pattern could be formed satisfactorily.

Example 7
In Example 2, the holding film of the core layer forming resin laminate is a polyimide film (product number; 4309, manufactured by Sumitomo 3M Co., Ltd.) with a re-peeling layer of 85 μm, and the holding film side is the outside and is rolled. A resin laminate was formed. I left it under sunlight for 1 hour. Then, when the optical waveguide was formed like Example 4 except having used the resin laminated body obtained above, the core pattern was able to be formed favorably.

Comparative Example 4
A resin laminate was formed in a roll shape with the cover film side of the clad layer forming resin laminate used in Comparative Example 1 facing outside. I left it under sunlight for 1 hour. Thereafter, except that the resin laminate obtained above was used, the resin layer for electrical wiring protection was formed in the same manner as in Example 3, and the resin layer was already cured and could not be developed.

Comparative Example 5
A resin laminate was formed in a roll shape with the cover film side of the resin laminate for forming a core layer used in Comparative Example 2 facing outside. I left it under sunlight for 1 hour. Thereafter, an optical waveguide was formed in the same manner as in Example 4 except that the resin laminate obtained above was used. As a result, the resin layer was already cured and the core pattern could not be developed.

  By using the method for laminating a resin layer of the present invention, it is easy to handle even a resin layer with a thin carrier film, and when the resin layer is laminated, a resin layer that is less likely to cause entrainment of bubbles and wrinkles can be formed. Therefore, it can be applied to a wide range of fields such as wiring boards (motherboards, semiconductor chip mounting boards), semiconductor packages, flexible boards, various optical devices, and optical interconnections.

Claims (13)

In a method of laminating a resin layer that bonds a resin layer to a subject,
Using the resin laminate in which the resin layer is formed on one surface of the carrier film and the holding film is provided on the surface opposite to the resin layer of the carrier film,
A method for laminating resin layers, wherein a resin layer surface of the resin laminate is bonded to the subject.   The method for laminating a resin layer according to claim 1, wherein the resin layer is a photosensitive resin layer.   The method for laminating a resin layer according to claim 2, wherein after the resin layer is bonded, the holding film is peeled off and the resin layer is exposed.   The method for laminating a resin layer according to claim 3, wherein after the resin layer is exposed, the carrier film is peeled off and the resin layer is developed.   The method for laminating a resin layer according to any one of claims 1 to 4, wherein the holding film is thicker than the carrier film.   The method for laminating a resin layer according to any one of claims 1 to 5, wherein the resin layer is a resin layer containing a radical photopolymerizable compound or / and a radical photopolymerization initiator.   The resin layer is at least one of a resist resin layer for forming an electric wiring, a resin layer for protecting an electric wiring, and a lower cladding layer, a core layer, and an upper cladding layer of an optical waveguide. The lamination method of the resin layer of description.   The method of laminating a resin layer according to any one of claims 1 to 7, wherein the subject is an uneven subject, and the unevenness is embedded in the resin layer by bonding the resin layer to the subject.   The method for laminating a resin layer according to any one of claims 1 to 8, wherein the bonding of the resin layer is performed by at least one of a roll laminator and a flat plate laminator.   It is a resin laminated body used for the lamination | stacking method of the resin layer in any one of the said Claims 1-9, Comprising: The resin layer is formed in one surface of a carrier film, and the said resin layer of the said carrier film is opposite A resin laminate having a holding film on the surface.   The resin laminate according to claim 10, further comprising a cover film on a surface of the resin layer opposite to the carrier film.   The resin laminate according to claim 11, wherein at least one of the carrier film and the cover film is a film that shields actinic rays for exposing the resin layer.   The resin laminate according to claim 11 or 12, wherein at least one of the carrier film, the cover film, and the holding film is a film that shields actinic rays for sensitizing the resin layer.