JP2005202066A - Light-sensitive transfer sheet, light-sensitive laminate, image pattern forming method, and wiring pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To easily form a desired pattern different in thickness within an image. <P>SOLUTION: A light-sensitive transfer sheet is used in which a first light-sensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator, a barrier layer containing a polymerizable compound, and a second light-sensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator and having a relatively higher light sensitivity than the first light-sensitive layer are laminated in this order on a support. An image is formed from a light-sensitive laminate in which the second light-sensitive layer containing the binder, polymerizable compound and photopolymerization initiator, the barrier layer containing the polymerizable compound, and the first light-sensitive layer containing the binder, polymerizable compound and photopolymerization initiator and having a relatively lower light sensitivity than the second light-sensitive layer are laminated in this order on a substrate. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photosensitive transfer sheet, a photosensitive laminate, an image pattern forming method, and a wiring pattern forming method. The present invention relates to a photosensitive transfer sheet, a laminate, and a method for forming a wiring pattern of a printed wiring board using the photosensitive transfer sheet or laminate particularly useful for producing a printed wiring board.

  Photosensitive transfer sheet with support and photosensitive layer is used for various image formation such as printed wiring boards, color filters, pillars, ribs, spacers, display members such as partition walls, printing plates, holograms, micromachines, and proofs. It is widely used as an image-like pattern forming material for manufacturing materials.

  In the field of manufacturing printed wiring boards, a wiring pattern is a photosensitive transfer sheet (also called dry film resist) comprising a transparent support (for example, polyethylene terephthalate) and a photosensitive layer formed on the support. It has been formed by photolithography technology. For example, in the case of manufacturing a printed wiring board having a through hole, a through hole is formed in a printed wiring board forming substrate (for example, a copper clad laminate), and a metal plating layer is formed on the inner side wall portion of the through hole. The photosensitive layer of the photosensitive transfer sheet is superposed and adhered to the surface, and the photosensitive layer is cured by irradiating each of the wiring pattern forming region and the region including the through-hole opening in a predetermined pattern. Next, the support of the photosensitive transfer sheet is peeled off, and a developer is used in the uncured area other than the cured area on the wiring pattern formation area and the cured area (called a tent film) on the through-hole opening area. Then, after dissolution and removal, an exposed metal layer portion is etched, and then a hardened region is removed to generate a wiring pattern on the substrate surface.

  A method of protecting the metal plating layer of the through hole using the tent film is generally called a tenting method. A multilayer printed wiring board may be provided with a hole for interlayer connection called a via hole. In this case as well, when forming a wiring pattern, it is necessary to protect the via hole portion with a tent film.

  In recent years, the demand for higher density in printed wiring boards has increased, and a photoresist film capable of higher resolution has been demanded. In order to increase the resolution of the photoresist film, it is effective to reduce the thickness of the photosensitive layer. However, as described above, the cured layer obtained by curing the photosensitive layer also serves to protect through holes or via holes formed in the printed wiring board. If the thickness of the photosensitive layer is simply reduced, the photosensitive resin composition In the process of dissolving and removing the uncured region of the object and the process of etching the exposed metal layer portion, there arises a problem that the tent film is broken.

  Hitherto, photosensitive transfer sheets that can form a high-resolution pattern and that can form a tent film that is not easily torn have been actively developed, and the results have been disclosed as follows.

  Patent Document 1 describes a photosensitive transfer sheet having a photosensitive layer composed of a binder component having a carboxyl group, a monomer component containing a specific vinylurethane compound and a specific acrylate compound, and a photopolymerization initiator.

  In Patent Document 2, a first photosensitive layer that is alkali-soluble and has low fluidity by heating and is sensitive to active energy rays is provided on a support, and further, it is alkali-soluble and has fluidity by heating. Largely, a photosensitive transfer sheet having a two-layered photosensitive layer provided with a second photosensitive layer sensitive to active energy rays is described. This patent document describes that the metal layer of the through hole can be protected by embedding the second photosensitive layer of the photosensitive transfer sheet in the through hole.

  Patent Document 3 discloses a photosensitive resin laminate having a first photosensitive layer and a second photosensitive layer on a support, the two layers having different vinyl copolymers, and both An example including a specific monofunctional monomer in the layer is described, and as an effect, it is described that adhesion and resolution are improved.

  Patent Document 4 describes a photoresist having a non-adhesive photosensitive layer and an adhesive photosensitive layer on a support, and a method for forming a printed wiring board using the photoresist. It is described that the performance and resolution are improved.

  In Patent Document 5, a printing relief having at least two photopolymerizable layers (having a thickness of 25 μm to 2.5 mm) having different photopolymerization speeds on a base material and having a high polymerization speed on the side close to the base material. A photosensitive plate for production is disclosed, and an example of forming a relief image in which the base of the printing surface is wider than the top is described.

Japanese Patent Laid-Open No. 10-142789 JP-A-8-54732 JP-A-10-111573 Japanese Patent Laid-Open No. 3-17650 Japanese Patent Publication No.37-1306

The subject of this invention is providing the photosensitive transfer sheet and photosensitive laminated body which can form easily the desired pattern from which thickness differs in an image.
Another object of the present invention is to provide a method capable of industrially advantageously forming desired patterns having different thicknesses in an image using a photosensitive transfer sheet or a photosensitive laminate.
An object of the present invention is to provide a photosensitive transfer sheet that is particularly effective for the production of printed wiring boards, can be increased in resolution by thinning, and can form a tent film that is not easily torn.
Another object of the present invention is to provide a method capable of industrially advantageously producing a printed wiring board having a hole portion such as a through hole or a via hole using a photosensitive transfer sheet.

  The present invention first includes a first photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator, a barrier layer containing a polymerizable compound, a binder, a polymerizable compound and a photopolymerization initiator on a support. The second photosensitive layer having a photosensitivity relatively higher than the photosensitivity of one photosensitive layer is in the photosensitive transfer sheet laminated in this order.

A preferred embodiment of the first invention is as follows.
(1) The barrier layer has photosensitivity, and the photosensitivity of the barrier layer is relatively lower than the photosensitivity of the first photosensitive layer.
(2) The polymerizable compound contained in the barrier layer is a polymer having a polymerizable group.
(3) The polymer having the polymerizable group of (2) has an affinity for water or a lower alcohol having 1 to 4 carbon atoms.
(4) The polymer having a polymerizable group of (3) is soluble in water or a lower alcohol having 1 to 4 carbon atoms.
(5) The barrier layer further contains a polymer having an affinity for water or a lower alcohol having 1 to 4 carbon atoms.
(6) The polymer of (5) is soluble in water or a lower alcohol having 1 to 4 carbon atoms.

(7) The barrier layer has a thickness in the range of 0.1 to 5 μm.
(8) When the photosensitivity of the first photosensitive layer is 1, the photosensitivity of the second photosensitive layer is in the range of 2 to 200.
(9) The ratio represented by A / B between the amount of light energy A necessary for curing the second photosensitive layer and the amount of light energy B necessary for curing the first photosensitive layer is 0.005. It is in the range of 0.5.
(10) The ratio represented by C / A between the amount of light energy A necessary for curing the second photosensitive layer and the amount of light energy C necessary until the first photosensitive layer is cured is 1 to 10 It is in the range.

(11) The amount of the photopolymerization initiator contained in the second photosensitive layer is larger than the amount of the photopolymerization initiator contained in the first photosensitive layer.
(12) The amount of the polymerizable compound contained in the second photosensitive layer is larger than the amount of the polymerizable compound contained in the first photosensitive layer.
(13) The first photosensitive layer has a thickness in the range of 1 to 100 μm, and the thickness is larger than the thickness of the second photosensitive layer.
(14) The second photosensitive layer has a thickness in the range of 0.1 to 15 μm.
(15) The support is made of synthetic resin and is transparent.
(16) The support is a long support.
(17) A protective film is disposed on the second photosensitive layer.
(18) It is a long body and is wound in a roll shape.
(19) For printed wiring board manufacture.

  The present invention secondly includes a second photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator on a substrate, a barrier layer containing a polymerizable compound, a binder, a polymerizable compound and a photopolymerization initiator. In the photosensitive laminate, the first photosensitive layer having a photosensitivity relatively lower than the photosensitivity of the photosensitive layer is laminated in this order.

A preferred embodiment of the second invention is as follows.
(1) The barrier layer has photosensitivity, and the photosensitivity of the barrier layer is relatively lower than the photosensitivity of the first photosensitive layer.
(2) The polymerizable compound contained in the barrier layer is a polymer having a polymerizable group.
(3) The polymer having the polymerizable group of (2) has an affinity for water or a lower alcohol having 1 to 4 carbon atoms.
(4) The polymer having a polymerizable group of (3) is soluble in water or a lower alcohol having 1 to 4 carbon atoms.
(5) The barrier layer further contains a polymer having an affinity for water or a lower alcohol having 1 to 4 carbon atoms.
(6) The polymer of (5) is soluble in water or a lower alcohol having 1 to 4 carbon atoms.

(7) The barrier layer has a thickness in the range of 0.1 to 5 μm.
(8) When the photosensitivity of the first photosensitive layer is 1, the photosensitivity of the second photosensitive layer is in the range of 2 to 200.
(9) The ratio represented by A / B between the amount of light energy A necessary for curing the second photosensitive layer and the amount of light energy B necessary for curing the first photosensitive layer is 0.005. It is in the range of 0.5.
(10) The ratio represented by C / A between the amount of light energy A necessary for curing the second photosensitive layer and the amount of light energy C necessary until the first photosensitive layer is cured is 1 to 10 It is in the range.

(11) The amount of the photopolymerization initiator contained in the second photosensitive layer is larger than the amount of the photopolymerization initiator contained in the first photosensitive layer.
(12) The amount of the polymerizable compound contained in the second photosensitive layer is larger than the amount of the polymerizable compound contained in the first photosensitive layer.
(13) The first photosensitive layer has a thickness in the range of 1 to 100 μm, and the thickness is larger than the thickness of the second photosensitive layer.
(14) The second photosensitive layer has a thickness in the range of 0.1 to 15 μm.
(15) The substrate is a printed wiring board forming substrate.
(16) A support (in particular, a transparent resin film is preferred) is laminated on the first photosensitive layer.
(17) For printed wiring board manufacture.

Thirdly, the present invention includes the following steps, on which a region where a cured resin layer formed by curing both the first photosensitive layer and the second photosensitive layer is present and a cured resin layer are not present. In this method, an image pattern including regions is formed.
(1) A step of laminating the photosensitive transfer sheet of the first invention on a substrate in a positional relationship such that the second photosensitive layer is on the substrate side;
(2) A step of performing light irradiation of a predetermined image pattern from the side of the first photosensitive layer of the laminate and curing both the first photosensitive layer and the second photosensitive layer in the region irradiated with the light;
(3) removing the support from the laminate; and
(4) The process of developing a laminated body and removing the unhardened part in a laminated body.

Fourthly, the present invention includes the following steps, a region where a resin layer formed by curing both the first photosensitive layer and the second photosensitive layer is present on the substrate, and the second photosensitive layer is cured. There is a method of forming an image pattern composed of a region where a resin layer is formed and a region where a cured resin layer is not present.
(1) A step of laminating the photosensitive transfer sheet of the first invention on a substrate in a positional relationship such that the second photosensitive layer is on the substrate side;
(2) Light irradiation is performed from the first photosensitive layer side of the laminate with an image pattern that defines a region to be irradiated with at least two different levels of irradiation energy amount, and the light irradiation energy amount is relatively large Curing both the first photosensitive layer and the second photosensitive layer in the region irradiated with light, and curing the second photosensitive layer in the region irradiated with light having a relatively small amount of light irradiation energy;
(3) removing the support from the laminate; and
(4) The process of developing a laminated body and removing the unhardened part in a laminated body.

Preferred embodiments of the third and fourth inventions of the present invention are as follows.
(1) The step of removing the support from the laminate of (3) is performed between step (1) and step (2) instead of between step (2) and step (4). .
(2) The light irradiation in the step (2) is performed by laser light irradiation.

Fifthly, the present invention includes a region covered with a cured resin layer formed by curing both the first photosensitive layer and the second photosensitive layer on a printed wiring board forming substrate including the following steps: And a method of forming a wiring pattern composed of a region where the substrate surface is exposed.
(1) A step of laminating the photosensitive transfer sheet of the first invention on a substrate in a positional relationship such that the second photosensitive layer is on the substrate side;
(2) A step of irradiating a predetermined wiring pattern from the first photosensitive layer side of the laminate and curing both the first photosensitive layer and the second photosensitive layer in the irradiated region;
(3) removing the support from the laminate; and
(4) The process of developing a laminated body and removing the unhardened part in a laminated body.

Sixth, the present invention includes a printed wiring board forming substrate having a hole portion, which includes the following steps, and is coated with a cured resin layer formed by curing both the first photosensitive layer and the second photosensitive layer. In this method, a wiring pattern is formed which includes a hole portion, a region covered with a cured resin layer formed by curing the second photosensitive layer, and a region where the substrate surface is exposed.
(1) A step of laminating the photosensitive transfer sheet of the first invention on a substrate in a positional relationship such that the second photosensitive layer is on the substrate side;
(2) From the side of the first photosensitive layer of the laminate, the hole portion is irradiated with light having a relatively large amount of light irradiation energy to cure both the first photosensitive layer and the second photosensitive layer, and wiring A step of irradiating the formation region with light of an image pattern that cures the second photosensitive layer by applying light irradiation with a relatively small amount of light irradiation energy;
(3) removing the support from the laminate; and
(4) The process of developing a laminated body and removing the unhardened part in a laminated body.

Preferred embodiments of the fifth and sixth inventions of the present invention are as follows.
(1) The step of removing the support from the laminate of (3) is performed between step (1) and step (2) instead of between step (2) and step (4). .
(2) The light irradiation in the step (2) is performed by laser light irradiation.

The photosensitive transfer sheet of the present invention can form cured layers having different thicknesses by changing the light irradiation amount (also referred to as exposure amount). Therefore, it is possible to change the thickness of the film only in a desired region (form a three-dimensional image), change the amount of transmitted light (change the density of the image), change the strength of the film, and the like. Therefore, for example, it is possible to form a pattern in which the thickness of the hardened layer is increased at a portion where the film strength is to be increased, and the thickness of the hardened layer is decreased at a portion where the resolution is to be increased. Therefore, when the photosensitive transfer sheet of the present invention is used for manufacturing a printed wiring board, particularly a printed wiring board having a hole portion such as a through hole or a via hole, the wiring pattern forming region has a relatively thin thickness. A resolution cured layer can be formed, and a relatively thick and high-strength cured layer can be formed in the through hole or via hole.
Further, by providing a barrier layer between the first photosensitive layer and the second photosensitive layer, mixing between the first photosensitive layer and the second photosensitive layer and migration of substances can be prevented, and the production of the photosensitive transfer sheet Is easy and there is little variation in sensitivity during storage. Furthermore, since the barrier layer also has polymerizability, the first photosensitive layer / barrier layer / in a process such as development in a portion where both the first photosensitive layer and the second photosensitive layer are cured (the portion where the cured film is thick). It is possible to prevent failures such as floating and peeling at any interface of the second photosensitive layer (especially easily occurring in a region having a small through-hole diameter). For this reason, a high-resolution printed wiring board can be manufactured by an industrially advantageous tenting method.

[Barrier layer]
The barrier layer is provided between the first photosensitive layer and the second photosensitive layer. The barrier layer has a function of preventing or controlling movement of components contained in the two photosensitive layers. The barrier layer may have a function of preventing or controlling movement of components contained in the photosensitive layer and the support or any other layer (for example, a protective film). The barrier layer can prevent the sensitivity of the photosensitive layer and the physical properties of each layer from changing due to the movement of the components. The barrier layer may further have a function of preventing the movement of an external substance (eg, oxygen) and a function of mitigating the influence of changes in external conditions (eg, humidity).
The barrier layer contains a polymerizable compound. The polymerizable compound is a compound having a polymerizable functional group, and includes a high molecular compound (oligomer or polymer) in addition to the low molecular compound (monomer). The barrier layer preferably contains both a low molecular weight polymerizable compound and a polymer (resin) that functions as a binder, or a high molecular weight polymerizable compound (resin) that functions as a binder.

  The polymerizable compound contained in the barrier layer is photopolymerized by the action of a photopolymerization initiator contained in the first photosensitive layer or the second photosensitive layer, or optionally a photopolymerization initiator contained in the barrier layer. The photopolymerization initiator contained in the barrier layer was one in which a part of the photopolymerization initiator contained in the first photosensitive layer or the second photosensitive layer moved to the barrier layer when the photosensitive transfer sheet was produced. May be. Therefore, the barrier layer can also have photosensitivity. However, the photosensitivity of the barrier layer is desirably lower than the photosensitivity of the first photosensitive layer (the order of the sensitivity is second photosensitive layer> first photosensitive layer> barrier layer).

The polymerizable functional group of the polymerizable compound is preferably a ring-opening polymerizable group or an addition polymerizable group, and more preferably an addition polymerizable group. The addition polymerizable group is particularly preferably an ethylenically unsaturated group.
The polymerizable compound preferably has a plurality of polymerizable functional groups in one molecule.

The low molecular weight polymerizable compound is the same as the polymerizable compound contained in the photosensitive layer described later. However, the low molecular weight polymerizable compound contained in the barrier layer preferably has an affinity for water or a lower alcohol having 1 to 4 carbon atoms, and for water or a lower alcohol having 1 to 4 carbon atoms. And more preferably soluble.
The binder used in combination with the low molecular weight polymerizable compound preferably has an affinity for a solvent (water or a lower alcohol having 1 to 4 carbon atoms). Affinity means having emulsification, dispersion, swelling, dissolution (including partial dissolution), and wettability with respect to the solvent. More preferably, the binder contained in the barrier layer is soluble in a solvent (water or a lower alcohol having 1 to 4 carbon atoms).
The mass ratio of the low molecular weight polymerizable compound to the binder (resin) is preferably 90:10 to 1:99, more preferably 70:30 to 5:95, and more preferably 60:40 to 5: 95 is most preferred.
Two or more kinds of low molecular weight polymerizable compounds may be used in combination. A low molecular weight polymerizable compound and a high molecular weight polymerizable compound (described below) may be used in combination.

A polymeric polymerizable compound (resin) that functions as a binder can be obtained by introducing a polymerizable functional group into a polymer that functions as a binder. Examples of the polymer that functions as a binder include examples of the binder contained in the photosensitive layer described later. However, the binder contained in the barrier layer is preferably different from the binder contained in the photosensitive layer and exhibits an affinity for a solvent (water or a lower alcohol having 1 to 4 carbon atoms). About affinity, it is as having demonstrated the binder used together with a low molecular weight polymeric compound.
The molecular weight of the polymer polymerizable compound is preferably 500 or more, and more preferably 1000 or more.

Examples of the polymer having an affinity for water or a lower alcohol having 1 to 4 carbon atoms include polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble polyamide, gelatin, and cellulose. Polyvinyl alcohol and modified polyvinyl alcohol are particularly preferred.
In order to introduce a polymerizable group into a polymer, a functional group (eg, carboxyl, sulfo, hydroxyl, acid halide group, acid anhydride structure, reactive to a functional group of the polymer (eg, hydroxyl, amino), A compound having a methylol group or an isocyanate group) and a polymerizable group may be reacted.

Examples of compounds having a carboxyl group (functional group reactive to polymer functional group, hereinafter abbreviated) and a polymerizable group are (meth) acrylic acid, itaconic acid, cinnamic acid, acrylic acid dimer, vinyl benzoate Includes acid, vinyloxybenzoic acid.
Examples of the compound having a sulfo group and a polymerizable group include 2-acrylamido-2-methylpropanesulfonic acid and styrenesulfonic acid.
Examples of the compound having a hydroxyl group and a polymerizable group include 2-hydroxyethyl (meth) acrylate.
Examples of the (cyclic) acid anhydride having a polymerizable group include maleic anhydride and itaconic anhydride. A compound in which an ethylenically unsaturated group is introduced into another acid anhydride (eg, phthalic anhydride, succinic anhydride) can also be used as a carboxyl group having a polymerizable group.
Examples of the compound having a methylol group and a polymerizable group include methylol (meth) acrylamide.
Examples of the compound having an isocyanate group and a polymerizable group are 2- (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, 1- (4-vinylphenyl) -1-methylethyl isocyanate, 1 -(4-Isopropenylphenyl) -1-methylethyl isocyanate.

As a polymeric polymerizable compound (resin) that functions as a binder, a water-soluble polyurethane resin having a polymerizable group (described in JP-A-3-168209 and JP-A-7-25958) may be used. A water-soluble polyurethane resin having a polymerizable group is obtained by reacting a carboxyl group-containing diol and polyoxyalkylene glycol with a polyisocyanate, and reacting a reaction product with a hydroxyl group-containing (meth) acrylate. It is obtained by neutralizing the carboxyl group therein with an amine. A water-soluble polyurethane resin having a polymerizable group can also be produced by reacting a polyol having a quaternary ammonium salt with a polyisocyanate and reacting a reaction product with a (meth) acrylate having a hydroxyl group. be able to.
An epoxy resin having a polymerizable group (described in JP-A-4-21413) may be used as a polymeric polymerizable compound (resin) that functions as a binder. The epoxy resin having a polymerizable group can be obtained by reacting an acid anhydride with epoxy acrylate and neutralizing with an amine.

A monomer having a functional group having an affinity for water or a lower alcohol having 1 to 4 carbon atoms (eg, vinylpyrrolidone) and a monomer having a plurality of polymerizable groups (eg, allyl (meth) acrylate) It may be copolymerized to leave a part of the polymerizable group contained in the latter monomer as the polymerizable group of the polymer.
A polymer obtained by reacting methacryloylethyl isocyanate with a copolymer of acryloylmorpholine and a hydroxyl group-containing (meth) acrylate (described in JP-A-9-146270) is also a polymer having a high molecular weight that functions as a binder. It can be used as a compound (resin).

Two or more kinds of polymer polymerizable compounds may be used in combination. You may use together a polymeric compound and another polymer (for example, poly (meth) acrylic acid ester, polyamide, polyester) which does not have a polymeric group. It is preferable that the polymer to be used in combination also exhibits affinity (or solubility) for water or a lower alcohol having 1 to 4 carbon atoms, like the polymer polymerizable compound.
The barrier layer is a component of a photosensitive layer described later (eg, photopolymerization initiator, sensitizer, thermal polymerization inhibitor, plasticizer, color former, colorant, pigment, conductive particles, filler, antifoaming agent, difficulty A flame retardant, a leveling agent, a peeling accelerator, an antioxidant, a fragrance, a thermal crosslinking agent, a surface tension adjusting agent, and a chain transfer agent). These optional components also preferably exhibit affinity (or solubility) for water or a lower alcohol having 1 to 4 carbon atoms. The barrier layer can also contain a thermoplastic resin (described in Japanese Patent No. 2794242).
The barrier layer preferably has a thickness in the range of 0.1 to 5 μm. Two or more barrier layers may be provided.

[Basic structure of photosensitive transfer sheet and photosensitive laminate]
As an example of the photosensitive transfer sheet of the present invention, a schematic cross-sectional view of a constitution having two photosensitive layers is shown in FIGS.

  In FIG. 1, a photosensitive transfer sheet 10 includes a support 11, a first photosensitive layer 12, a barrier layer 13, and a second photosensitive layer 14 laminated in this order. The first photosensitive layer 12 and the second photosensitive layer 14 are each composed of a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator, and are cured by light irradiation. The photosensitive transfer sheet of the present invention is mainly characterized in that the second photosensitive layer 14 has relatively higher photosensitivity than the first photosensitive layer 12. Here, the photosensitivity corresponds to the amount of light energy required to cure each photosensitive layer, and the high photosensitivity means that the second photosensitive layer 14 is cured less than the first photosensitive layer 12. It means that starting with a light irradiation amount or curing of the second photosensitive layer 14 is completed with a light irradiation amount smaller than that of the first photosensitive layer 12.

  FIG. 2 is a photosensitive transfer sheet in which a protective film 15 is further laminated on the photosensitive transfer sheet of FIG.

  The thicknesses of the first photosensitive layer, the barrier layer and the second photosensitive layer can be arbitrarily set according to the purpose. However, the first photosensitive layer preferably has a thickness in the range of 1 to 100 μm, more preferably in the range of 5 to 80 μm, and particularly preferably in the range of 10 to 50 μm. When the thickness of the first photosensitive layer is less than 1 μm, it may be inappropriate to increase the film strength, and when the thickness exceeds 100 μm, development problems such as development residue remaining easily occur. There is. The thickness of the first photosensitive layer is preferably larger than the thickness of the second photosensitive layer.

  The barrier layer preferably has a thickness in the range of 0.1 to 5 μm, more preferably in the range of 0.5 to 4 μm, and particularly preferably in the range of 1 to 3 μm. If the thickness of the barrier layer is less than 0.1 μm, sufficient barrier properties may not be obtained. If the thickness exceeds 5 μm, it takes a long time for development. The second photosensitive layer preferably has a thickness in the range of 0.1 to 15 μm, more preferably in the range of 1 to 12 μm, and particularly preferably in the range of 3 to 10 μm. If the thickness of the second photosensitive layer is less than 0.1 μm, uneven thickness is likely to occur during coating, and if the thickness exceeds 15 μm, the resolution is lowered.

  The layer configuration of the photosensitive transfer sheet of the present invention is not limited to the layer configuration illustrated in FIGS. 1 and 2 above, and may have layers other than the layers illustrated in FIGS. 1 and 2. . For example, between the support 11 and the first photosensitive layer 12, or between the protective film 15 and the second photosensitive layer 14, a layer for adjusting the peelability and adhesion between the support and the substrate, an antihalation layer, Alternatively, a barrier layer or the like may be provided. In this case, the barrier layer has a role of preventing or suppressing migration of substances contained in the photosensitive layer, the support, or the protective film, and preventing or suppressing external influences such as oxygen and humidity.

  Next, the relationship between the light irradiation amount and the photosensitive layer curing amount in the photosensitive transfer sheet and photosensitive laminate of the present invention will be described with reference to FIG. In FIG. 3, for example, the photosensitive transfer sheet shown in FIG. 1 or the photosensitive transfer sheet from which the protective film is peeled off from the photosensitive transfer sheet shown in FIG. 2 is transferred onto a substrate to form a laminate. In the case where the photosensitive layer is irradiated with light from the opposite side of the substrate from the side opposite to the substrate through the support, or if necessary, the support is peeled off. 2 is a graph (sensitivity curve) showing the relationship between the light irradiation amount, the irradiation (exposure), and the thickness of the cured layer generated by the subsequent development processing. In FIG. 3, the horizontal axis represents the amount of light irradiation, and the vertical axis represents the thickness of the cured layer obtained after being cured by light irradiation and developed. D on the vertical axis is the thickness of the cured layer formed from the second photosensitive layer, E is the total thickness of the cured layer and the barrier layer formed from the first photosensitive layer, and F is the thickness of the first photosensitive layer. It represents the total thickness of the thickness of the cured layer formed from one photosensitive layer, the thickness of the barrier layer, and the thickness of the cured layer formed from the second photosensitive layer.

  As shown in FIG. 3, in the photosensitive transfer sheet of the present invention, the light irradiated from the support side proceeds in the order of the support, the first photosensitive layer, the barrier layer, and the second photosensitive layer when the support is provided. Nevertheless, curing of the second photosensitive layer begins with a small amount of light energy prior to the first photosensitive layer. Then, after the entire second photosensitive layer is cured, when the amount of light energy is increased, curing of the first photosensitive layer starts, and when the amount of light energy is further increased, the entire first photosensitive layer is cured.

  Regarding the relationship between the sensitivity of the first photosensitive layer and the sensitivity of the second photosensitive layer, when the photosensitivity of the first photosensitive layer is 1, the photosensitivity of the second photosensitive layer is preferably in the range of 2 to 200. More preferably, it is in the range of 2.5 to 100, and particularly preferably in the range of 3 to 50.

  The amount of light energy C required until the curing of the first photosensitive layer may be the same as the amount of light energy A necessary to cure the second photosensitive layer, but is greater than the amount of light energy A. Is preferred.

  As in the case of the photosensitive transfer sheet shown in FIG. 1, the film thickness E in the case of having a barrier layer between the first photosensitive layer and the second photosensitive layer is the thickness of the cured layer formed from the first photosensitive layer. And the thickness of the hardened layer formed from the second photosensitive layer plus the thickness of the barrier layer.

  The photosensitive transfer sheet of the present invention may have two or more photosensitive layers. As an example, FIG. 4 shows a cross-sectional view when the photosensitive layer has three layers. And the case where it has a protective film on the photosensitive layer of FIG. 4 is shown in FIG.

  In the photosensitive transfer sheet 50 of FIGS. 4 and 5, the support is represented by 51, and the first photosensitive layer 52, the barrier layer 53, the second photosensitive layer 54, and the barrier layer are formed on the support 51. 53 and a third photosensitive layer 55 are sequentially laminated. FIG. 5 shows a configuration in which a protective film 56 is provided on the photosensitive transfer sheet of FIG.

  Even in the case of these three photosensitive layer configurations, each photosensitive layer has a relatively higher sensitivity of the photosensitive layer on the side farther from the support than the sensitivity of the photosensitive layer on the side closer to the support. That is, the sensitivity of the photosensitive layer is the highest for the third photosensitive layer, then the second photosensitive layer is the highest, and the sensitivity of the first photosensitive layer is the lowest.

  The photosensitive transfer sheet having the structure shown in FIGS. 4 and 5 is used, and the amount of light energy used for pattern formation is set to a light energy amount X for curing only the third photosensitive layer in accordance with a required region. The amount of light energy Y for curing the first and second photosensitive layers, the amount of light energy Z for curing all of the third photosensitive layer, the second photosensitive layer, and the first photosensitive layer, and the amount of light irradiation. Thus, as shown in FIG. 6, a region having a thickness obtained by curing only the third photosensitive layer, a region having a thickness obtained by curing the third photosensitive layer and the second photosensitive layer, a third photosensitive layer, It is possible to form a pattern having three different thicknesses, that is, a region having a cured thickness of the second photosensitive layer and the first photosensitive layer, with one type of photosensitive transfer sheet.

  Similarly, the photosensitive layer has N layers (the number of photosensitive layers is N), and the sensitivity of the photosensitive layer on the side away from the support is relatively higher than the sensitivity of the photosensitive layer on the side close to the support. If a transfer sheet is used, it becomes possible to form a cured layer pattern having different thicknesses in N stages with a single type of photosensitive transfer sheet.

  As described above, in the photosensitive transfer sheet of the present invention, the thickness of the cured layer obtained by exposure and development processing can be set to a desired thickness according to the exposure amount (so-called light energy amount). It is possible, and by changing the pattern of exposure amount as necessary, it is possible to create from the region where only the photosensitive layer closest to the substrate is cured to the region where all the photosensitive layers are cured by changing the thickness sequentially Is possible. Therefore, 3D modeling with different thicknesses inside the image, a cured resin image with characteristics such as increasing the strength of the film only in the desired area, or increasing the image density only in the desired area, etc. It can be formed with a photosensitive transfer sheet.

  Therefore, when the photosensitive transfer sheet of the present invention is used for the production of a printed wiring board, particularly for the production of a printed wiring board having a through hole or a via hole, the wiring pattern formation region is relatively thin and has a high resolution. A hardened layer is formed, and a high-strength hardened layer having a relatively thick thickness can be formed in the through hole or via hole. Therefore, by using the photosensitive transfer sheet of the present invention, it is possible to easily form a cured resin pattern having sufficient tent film strength that can be used as a tenting method and having sufficient resolution in a portion requiring high resolution. Can do.

  According to the present invention, the photosensitive transfer sheet having the sensitivity curve as described above can be realized by relatively increasing the sensitivity of each photosensitive layer in order from the side closer to the support toward the side away from the support. found. Any known high sensitivity technology can be used as a method of making the photosensitive layer into two or more layers and increasing the sensitivity of the photosensitive layers sequentially in order. That is, for example, use of a high-sensitivity initiator, use of a sensitizer, increase in the content of a photopolymerization initiator and / or sensitizer, or increase the content of a polymerizable compound in the photosensitive layer, polymerization inhibition It can be obtained by a technique such as reducing the ratio of the agent or the polymerization inhibitor. In particular, when the photosensitive layer has two layers, for example, a high-sensitivity initiator is used, and a sensitizer is added to the second photosensitive layer, and a photopolymerization initiator and / or sensitizer in the second photosensitive layer. Can be obtained by a technique such as increasing the content of the first photosensitive layer or increasing the content of the polymerizable compound in the second photosensitive layer than that of the first photosensitive layer.

On the support of the present invention, a first photosensitive layer comprising a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator, a barrier layer, and a binder, a polymerizable compound, and a photopolymerization initiator. An image pattern (cured resin pattern) using a photosensitive transfer sheet comprising a photosensitive resin composition comprising a second photosensitive layer having a photosensitivity relatively higher than that of the first photosensitive layer. when forming a), light energy amount S the curing of the second photosensitive layer begins, preferably in the range of 0.05~10mJ / cm ^2, further the range of 0.1~5mJ / cm ² Is preferable, and it is particularly preferable to be in the range of 0.15 to 2.5 mJ / cm ² . The amount of light energy A necessary for curing the second photosensitive layer is preferably in the range of 0.1~20mJ / cm ^2, that further the range of 0.2~15mJ / cm ² preferably In particular, the range of 0.4 to 10 mJ / cm ² is preferable.

The ratio (A / B) of the amount of light energy A required to cure the second photosensitive layer and the amount of light energy B necessary to cure the first photosensitive layer is in the range of 0.005 to 0.5. It is preferably in the range of 0.01 to 0.4, and more preferably in the range of 0.02 to 0.35. The ratio (C / A) of the amount of light energy A required to cure the second photosensitive layer and the amount of light energy C necessary until the first photosensitive layer begins to be cured (C / A) is in the range of 1 to 10. Is more preferable, and it is preferable that it exists in the range of 1.1-9, and it is especially preferable that it is the range of 1.3-8. The optical energy C is preferably in the range of 0.1~200mJ / cm ^2, that further in the range of 1 to 100 mJ / cm ² is preferred, particularly from 2~50mJ / cm ² It is preferable.

  Next, each material used for the photosensitive transfer sheet of this invention and the photosensitive layer of a photosensitive laminated body is demonstrated.

[binder]
The binder used in each photosensitive layer is preferably soluble in an alkaline aqueous solution, or preferably has at least swelling property. Examples of such binders include those having an acidic group (carboxyl group, sulfonic acid group, phosphoric acid group, etc.). Particularly, binders having a carboxyl group are typical, for example, a carboxyl group-containing vinyl copolymer. Polymers, carboxyl group-containing polyurethane resins, polyamic acid resins, modified epoxy resins, etc. are mentioned, but carboxyls are used because of their solubility in coating solvents, solubility in alkaline developers, suitability for synthesis, and ease of adjustment of film properties. A group-containing vinyl copolymer is preferred.

  The carboxyl group-containing vinyl copolymer can be obtained by copolymerization with at least (1) a carboxyl group-containing vinyl monomer and (2) a monomer copolymerizable therewith.

  Examples of the carboxyl group-containing vinyl monomer include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, and the like. Also, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, (meth) acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, and the like.

  Other copolymerizable monomers that can be used for the synthesis of the above copolymer are not particularly limited, and examples of such monomers include (meth) acrylic acid esters, crotonic acid esters, Vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth) acrylonitrile and the like are preferred. Examples of such a compound include the following compounds.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth). Acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, t-octyl (meth) acrylate, dodecyl (Meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, -Ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol Monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol mono Ethyl ether (meth) acrylate, β-phenoxyethoxyethyl acrylate, nonyl phen Noxypolyethylene glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) Examples thereof include acrylate, perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, and tribromophenyloxyethyl (meth) acrylate.

  Examples of crotonic acid esters include butyl crotonate and hexyl crotonate. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate. Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate. Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

  Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene. Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  In addition to the above compounds, (meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (eg, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinyl Caprolactone and the like can also be used.

  Further, 2-acrylamido-2-methylpropanesulfonic acid, mono (2-acryloyloxyethyl ester) phosphate, mono (1-methyl-2-acryloyloxyethyl ester) phosphate, and the like can also be used.

  In addition to the above compounds, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used. Such a monomer having a urethane group or a urea group can be appropriately synthesized using, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group containing It can be appropriately synthesized by an addition reaction between a monomer and monoisocyanate.

Specific examples of the isocyanate group-containing monomer include the following compounds (R ¹ represents a hydrogen atom or a methyl group).

  Specific examples of the monoisocyanate include cyclohexyl isocyanate, n-butyl isocyanate, toluyl isocyanate, benzyl isocyanate, and phenyl isocyanate.

Specific examples of the hydroxyl group-containing monomer include the following compounds (R ¹ represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more).

  Examples of the compound containing one hydroxyl group include alcohols (methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-hexanol, 2-ethylhexanol, n-decanol, n-dodecanol, n-octadecanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenylethyl alcohol, etc.), phenols (phenol, cresol, naphthol, etc.), and further containing substituents such as fluoroethanol, tri Examples include fluoroethanol, methoxyethanol, phenoxyethanol, chlorophenol, dichlorophenol, methoxyphenol, and acetoxyphenol.

  Examples of the primary or secondary amino group-containing monomer include, for example, vinylbenzylamine.

  Specific examples of compounds containing one primary or secondary amino group include alkylamines (methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, t-butylamine, hexyl). Amine, 2-ethylhexylamine, decylamine, dodecylamine, octadecylamine, dimethylamine, diethylamine, dibutylamine, dioctylamine), cyclic alkylamine (cyclopentylamine, cyclohexylamine, etc.), aralkylamine (benzylamine, phenethylamine, etc.), Arylamine (aniline, toluylamine, xylylamine, naphthylamine, etc.), a combination thereof (N-methyl-N-benzylamine, etc.), and an amine further containing a substituent (trifluoroethyl) Min, hexafluoro isopropyl amine, methoxyaniline, and methoxy propylamine, etc.) and the like.

  The above compounds may be used alone or in combination of two or more. Examples of other particularly preferred monomers are methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, styrene, chlorostyrene. , Bromostyrene, and hydroxystyrene.

  Such a vinyl copolymer can be obtained by copolymerizing corresponding monomers according to a conventional method according to a conventional method. For example, it can be obtained by using a method (solution polymerization method) in which these monomers are dissolved in a suitable solvent and a radical polymerization initiator is added thereto to polymerize in a solution. Further, polymerization may be carried out by so-called emulsion polymerization or the like in a state where the above monomer is dispersed in an aqueous medium.

  Examples of suitable solvents used in the solution polymerization method can be arbitrarily selected depending on the monomers used and the solubility of the copolymer to be produced. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, and toluene can be mentioned. These solvents may be used as a mixture of two or more. Examples of radical polymerization initiators include azo compounds such as 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile), benzoyl par Peroxides such as oxides, and persulfates such as potassium persulfate and ammonium persulfate can be used.

  The content of the repeating unit derived from the polymerizable compound having a carboxyl group in the vinyl copolymer obtained from these monomers is preferably 5 to 50 mol% in all the repeating units of the copolymer for each photosensitive layer, More preferably, it is 10-40 mol%, and 15-35 mol% is especially preferable. If the content is less than 5 mol%, the developability to alkaline water may be insufficient, and if it exceeds 50 mol%, the developer resistance of the cured portion (image portion) may be insufficient.

  The molecular weight of the binder having a carboxyl group can be arbitrarily adjusted, but the weight average molecular weight of each photosensitive layer is preferably 2000 to 300000, particularly preferably 4000 to 150,000. When the mass average molecular weight is less than 2000, the strength of the film tends to be insufficient, and stable production tends to be difficult. On the other hand, if the molecular weight exceeds 300,000, the developability tends to decrease.

  These binders having a carboxyl group may be used alone or in combination of two or more binders in each photosensitive layer. Examples of using two or more binders in combination include two or more binders composed of different copolymerization components, two or more binders having different mass average molecular weights, and two or more binders having different dispersities. .

  In the binder having a carboxyl group, part or all of the carboxyl group may be neutralized with a basic substance. As the binder, resins having different structures such as polyester resin, polyamide resin, polyurethane resin, epoxy resin, polyvinyl alcohol, and gelatin may be used in combination.

  Examples of the binder include resins soluble in an alkaline aqueous solution described in Japanese Patent No. 2873889 and the like.

  The content of the binder in the photosensitive layer is usually 10 to 90% by mass, preferably 20 to 80% by mass, and particularly preferably 40 to 80% by mass in each photosensitive layer. When the content of the binder having a carboxyl group (and a polymer binder used in combination as necessary) is small, alkali developability and adhesion to a printed wiring board forming substrate (for example, a copper-clad laminate) are obtained. If the amount tends to decrease and increases too much, the stability with respect to the development time and the strength of the cured film (tent film) tend to decrease. In order to adjust the sensitivity, the content of the binder contained in the second photosensitive layer within the above range is lower than the content of the binder contained in the first photosensitive layer (the content of the polymerizable compound is increased). You may make adjustments.

[Polymerizable compound]
A polymerizable compound (so-called monomer) is used for the photosensitive layer, and it is particularly preferable to use a monomer or oligomer (polyfunctional monomer or polyfunctional oligomer) containing two or more polymerizable groups. As the polymerizable group, an ethylenically unsaturated bond (for example, (meth) acryloyl group, (meth) acrylamide group, styryl group, vinyl group such as vinyl ester and vinyl ether, allyl group such as allyl ether and allyl ester), and the like can be polymerized. And cyclic ether groups (for example, epoxy groups, oxetane groups, etc.). Of these, ethylenically unsaturated bonds are preferred.

  Examples of such polyfunctional monomers include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with aliphatic polyhydric alcohol compounds, unsaturated Examples include amides of carboxylic acids and polyvalent amine compounds.

  Specific examples of an ester monomer of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include (meth) acrylic acid ester, ethylene glycol di (meth) acrylate, and polyethylene glycol having 2 to 18 ethylene groups. Di (meth) acrylate (for example, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, dodecaethylene glycol di (meth) acrylate, Tetradecaethylene glycol di (meth) acrylate), propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate having 2 to 18 propylene groups (for example, Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, dodecapropylene glycol di (meth) acrylate, etc.), neopentyl glycol di (meth) acrylate, ethylene oxide modified neo Pentyl glycol di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) Ether, trimethylolethane tri (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,3-butanediol (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,5-pentanediol (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate Rate, sorbitol hexa (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate , An alkylene glycol chain di (meth) acrylate having at least one ethylene glycol chain / propylene glycol chain (for example, compounds described in WO01 / 98832), ethylene oxide and / or trimethylol to which propylene oxide is added Propane tri (meth) acrylate, polybutylene glycol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, key Examples include silenol di (meth) acrylate.

  Among the above (meth) acrylic acid esters, preferred examples include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and polypropylene glycol diene because of their availability. (Meth) acrylate, di (meth) acrylate of alkylene glycol chain having at least one ethylene glycol chain / propylene glycol chain, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol triacrylate , Pentaerythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, g Serine tri (meth) acrylate, diglycerin di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, Examples include 1,5-pentanediol (meth) acrylate, neopentyl glycol di (meth) acrylate, and tri (meth) acrylic acid ester of trimethylolpropane added with ethylene oxide.

  Examples of esters of itaconic acid and aliphatic polyhydric alcohol compounds (itaconic acid esters) include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, and 1,4-butanediol. Examples include diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetritaconate.

  Examples of esters of crotonic acid and aliphatic polyhydric alcohol compounds (crotonate esters) include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. .

  Examples of esters of isocrotonic acid and aliphatic polyhydric alcohol compounds (isocrotonate) include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of esters of maleic acid and aliphatic polyhydric alcohol compounds (maleic acid esters) include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of amides derived from polyvalent amine compounds and unsaturated carboxylic acids include methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, 1,6-hexamethylene bis (meth) acrylamide, octamethylene bis ( Examples include meth) acrylamide, diethylenetriamine tris (meth) acrylamide, diethylenetriamine bis (meth) acrylamide, and xylylene bis (meth) acrylamide.

  Furthermore, 2,2-bis [4- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] propane having a bisphenol skeleton, 2,2-bis [4-((meth) acryloxyethoxy) phenyl] Propane, 2,2-bis (4-((meth) acryloyloxypolyethoxy) phenyl) propane having 2 to 20 ethyleneoxy groups substituted with one phenolic OH group (for example, 2,2-bis ( 4-((meth) acryloyloxydiethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxy) Pentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxydecaethoxy) phenyl) propyl Bread, 2,2-bis (4-((meth) acryloyloxypentadecaethoxy) phenyl) propane), 2,2-bis [4-((meth) acryloxypropoxy) phenyl] propane, phenolic OH 2,2-bis (4-((meth) acryloyloxypolypropoxy) phenyl) propane having 2 to 20 propyleneoxy groups substituted on one group (for example, 2,2-bis (4-((meth)) Acryloyloxydipropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentapropoxy) phenyl) propane 2,2-bis (4-((meth) acryloyloxydecapropoxy) phenyl) propane, 2, -Bis (4-((meth) acryloyloxypentadecapropoxy) phenyl) propane, etc.) and compounds containing both a polyethylene oxide skeleton and a polypropylene oxide skeleton in the same molecule as the polyether moiety of these compounds are also mentioned ( For example, compounds described in WO01 / 98832). These compounds can be obtained, for example, as BPE-200, BPE-500, BPE-1000 (manufactured by Shin-Nakamura Chemical Co., Ltd.).

  In addition, compounds having an isocyanate group and a polymer group (2-isocyanate ethyl (meth) acrylate, α, α- A polymerizable compound having a bisphenol skeleton and a urethane group, such as an adduct of dimethyl-vinylbenzyl isocyanate and the like, can also be used.

In addition, novolak type epoxy resin, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylol A compound obtained by adding an α, β-unsaturated carboxylic acid to a glycidyl group-containing compound such as propanetriglycidyl ether, pentaerythritol tetraglycidyl ether, bisphenol A diglycidyl ether, or glycerin triglycidyl ether can also be used.

  Moreover, the compound containing a polymeric group and a urethane group can also be utilized. Examples of such compounds are described in JP-B-48-41708, JP-A-51-37193, JP-B-5-50737, JP-B-7-7208, JP-A-2001-154346, JP-A-2001-356476, and the like. For example, a polyisocyanate compound having two or more isocyanate groups per molecule (for example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, norbornene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-diphenyl diisocyanate, burettes and isocyanurates of these diisocyanates Any trimer, adducts of these diisocyanates with polyfunctional alcohols such as trimethylolpropane, pentaerythritol, and glycerin, or polyfunctional alcohols such as ethylene oxide adducts) and hydroxyl groups in the molecule. Containing vinyl monomer (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene Glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate Trimethylolpropane di (meth) acrylate, vinyl urethane compounds containing two or more polymerizable vinyl groups per molecule obtained by allowed to addition of pentaerythritol tri (meth) acrylate, etc.) and the like. In addition, compounds having an isocyanurate ring such as tri ((meth) acryloyloxyethyl) isocyanurate, di (meth) acrylated isocyanurate, and tri (meth) acrylate of ethylene oxide-modified isocyanuric acid can also be used.

  Further, polyester acrylates, polyester (meth) acrylate oligomers, and epoxy compounds (novolak type epoxy resins) as described in JP-A-48-64183, JP-B-49-43191, and JP-B-52-30490. , Butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, bisphenol A diglycidyl ether, glycerin triglycidyl ether, etc.) and (meth) acrylic acid reacted with epoxy acrylates, etc. Functional acrylate or methacrylate can be mentioned. Moreover, the esterified substance etc. which are obtained from a vinyl monomer which contains a hydroxyl group in the said molecule | numerator with a phthalic acid, trimellitic acid, etc. are mentioned. Furthermore, what is introduce | transduced as a photocurable monomer and an oligomer by the Japan Adhesive Association magazine vol.20, No.7, 300-308 pages (1984) can also be used.

  Also, allyl esters (eg, diallyl phthalate, diallyl adipate, diallyl malonate, diallyl phthalate, triallyl trimellitic acid, diallyl benzenedisulfonate, triallyl isocyanurate); and diallylamides (eg, diallylacetamide) Available.

  Further, cationically polymerizable divinyl ethers (for example, butanediol-1,4-divinyl ether, cyclohexane dimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, dipropylene glycol divinyl ether, hexanediol divinyl ether) , Trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, bisphenol A divinyl ether, glycerin trivinyl ether, etc.), epoxy compounds (novolac type epoxy resin, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol) Diglycidyl ether, diethylene glycol diglycidyl ether , Dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, bisphenol A diglycidyl ether, glycerin triglycidyl ether, etc.), oxetanes (for example, 1,4-bis [ (3-ethyl-3-oxetanylmethoxy) methyl] benzene etc.) can also be used. Moreover, as an epoxy compound and oxetanes, the compound of WO01 / 22165 can also be used.

Examples of vinyl esters include divinyl succinate, divinyl adipate, divinyl phthalate, divinyl terephthalate, divinyl benzene-1,3-disulfonate, divinyl butane-1,4-disulfonate, and the like.
Examples of the styrene compound include divinylbenzene, 4-allylstyrene, 4-isopropenestyrene, and the like.

  In addition, different ethylenic unsaturations such as N-β-hydroxyethyl-β- (methacrylamide) ethyl acrylate, N, N-bis (β-methacryloxyethyl) acrylamide, allyl methacrylate, etc., other than the above compounds A compound having two or more double bonds can also be mentioned as a compound suitably used in the present invention.

  These polyfunctional monomers and oligomers can be used alone or in combination of two or more.

  Furthermore, if necessary, a polymerizable compound (monofunctional monomer) containing one polymerizable group in the molecule can be used in combination. Examples of the monofunctional monomer include the compounds exemplified as the raw material of the above-mentioned binder, a dibasic mono ((meth) acryloyloxyalkyl ester) mono (halohydroxyalkyl ester) disclosed in JP-A-6-236031 Monofunctional monomers such as γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate, etc., and compounds described in Japanese Patent No. 2744463, WO00 / 52529, Japanese Patent No. 2548016, etc. Is given.

  The content of the monomer in the photosensitive layer is generally in the range of 5 to 90% by mass for each photosensitive layer, preferably in the range of 15 to 60% by mass, and particularly preferably in the range of 20 to 50% by mass. If the monomer content is less than the above range, the strength of the tent film is lowered, and if it is greater, the edge fusion during storage (exudation failure from the end of the roll) tends to deteriorate. Moreover, content of the polyfunctional monomer containing 2 or more polymerizable groups among all monomers is generally in the range of 5 to 100% by mass, preferably in the range of 20 to 100% by mass, and more preferably 40 to 40% by mass. The range is 100% by mass. In order to adjust the sensitivity, adjustment such as increasing the monomer content of the second photosensitive layer within the above range may be performed.

[Photopolymerization initiator]
As the photopolymerization initiator used in the photosensitive transfer sheet of the present invention, any compound having the ability to initiate the polymerization of the above-described monomer components can be used, and is particularly sensitive to visible light from the ultraviolet region. Any material can be suitably used. The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm). The photopolymerization initiator may also be an activator that generates an active radical by generating some action with the photoexcited sensitizer, and is an initiator that initiates cationic polymerization depending on the type of monomer. Also good.

  Photopolymerization initiators preferably used in the photosensitive layer include, for example, halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), hexaarylbiimidazoles, oxime derivatives, organic peroxidation. Products, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers and the like. Of these, the use of a halogenated hydrocarbon having a triazine skeleton, an oxime derivative, hexaarylbiimidazole, and a ketone compound is particularly sensitive to the sensitivity and storability of the photosensitive layer and the adhesion between the photosensitive layer and the printed wiring board forming substrate. From the viewpoint of the above.

Examples of the halogenated hydrocarbon compound having a triazine skeleton include the following compounds.
Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), for example, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4 -Chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-tolyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 -(4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -1, 3,5-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- n-nonyl-4,6-bis (trichloromethyl) -1,3 - triazine, and 2-(alpha, alpha, beta-trichloroethyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  Compounds described in GB 1388492, for example, 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4,6-bis (trichloro) Methyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (4-methoxystyryl) -4- Amino-6-trichloromethyl-1,3,5-triazine.

  Compounds described in JP-A-53-133428, for example, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4 -Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (Acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  Compounds described in DE 33 37 024, for example, 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-methoxystyryl) ) Phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (1-naphthylvinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-thiophen-2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3 , 5-triazine, 2- (4-thiophene-3-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-furan-2-vinylenef Nyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (4-benzofuran-2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine.

  FC Schaefer et al., J. Org. Chem .; 29, 1527 (1964) described compounds such as 2-methyl-4,6-bis (tribromomethyl) -1,3,5-triazine, 2,4, 6-tris (tribromomethyl) -1,3,5-triazine, 2,4,6-tris (dibromomethyl) -1,3,5-triazine, 2-amino-4-methyl-6-tri (bromomethyl) ) -1,3,5-triazine and 2-methoxy-4-methyl-6-trichloromethyl-1,3,5-triazine.

  Compounds described in JP-A-62-258241, for example, 2- (4-phenylethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-naphthyl-1) -Ethynylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-tolylethynyl) phenyl) -4,6-bis (trichloromethyl) -1,3 5-triazine, 2- (4- (4-methoxyphenyl) ethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-isopropylphenylethynyl) phenyl ) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-ethylphenylethynyl) phenyl) -4,6-bis (trichloromethyl) -1, , 5-triazine.

  Compounds described in JP-A-5-281728, for example, 2- (4-trifluoromethylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,6-difluorophenyl) ) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,6-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,6-Dibromophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

  2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -1,3,5-triazine described in JP-A-5-34920, Trihalomethyl-s-triazine compounds described in U.S. Pat. No. 4,239,850, 2,4,6-tris (trichloromethyl) -s-triazine, 2- (4-chlorophenyl) -4,6-bis (Tribromomethyl) -s-triazine and the like.

  In addition, compounds having an oxadiazole skeleton described in US Pat. No. 4,221,976 can be used. Examples of the compound having an oxadiazole skeleton include 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadi Azole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (2-naphthyl) -1,3,4-oxadiazole, 2- Tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxy) Styryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) ) -1,3,4-oxadiazole, 2-tripromomethyl-5-styryl-1,3,4-oxadiazole, and the like.

  Examples of the oxime derivative that can be suitably used in the present invention include compounds represented by the following general formula.

  Examples of the hexaarylbiimidazole that can be used in the present invention include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2 -Fluorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2, 2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (3-methoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (4-methoxyphenyl) biimidazole, 2,2′-bis (4- Methoxypheni ) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (2-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole Examples include imidazole, 2,2′-bis (2-trifluoromethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and compounds described in WO 00/52529.

  The above biimidazoles can be easily synthesized by, for example, the methods disclosed in Bull. Chem. Soc. Japan, 33,565 (1960), and J. Org. Chem, 36 (16) 2262 (1971). it can.

  Examples of ketone compounds include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxy. Carbonyl benzolphenone, benzophenone tetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bisdicyclohexylamino) Benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzophenone 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro-thioxanthone 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1 -Propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (eg benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether) Ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - chloro acridone and the like.

  In addition, acridine derivatives (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine, and the like, polyhalogen compounds (for example, carbon tetrabromide, phenyltribromo, etc.) Methylsulfone, phenyltrichloromethyl ketone, etc.), coumarins (eg, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7 -Diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3'-carbonylbis (5,7-di-n-propoxy) Coumarin), 3,3′-carbonylbis (7-diethylaminocoumarin) ), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridyl) Carbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, and the like, and in addition, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206. No., JP-A No. 2002-363207, JP-A No. 2002-363208, JP-A No. 2002-363209, etc.), amines (for example, ethyl 4-dimethylaminobenzoate, 4-dimethyl N-butyl aminobenzoate, phenethyl 4-dimethylaminobenzoate, 4-dimethyla Minobenzoic acid 2-phthalimidoethyl, 4-dimethylaminobenzoic acid 2-methacryloyloxyethyl, pentamethylenebis (4-dimethylaminobenzoate), phenethyl and pentamethylene ester of 3-dimethylaminobenzoic acid, 4-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylaminobenzyl alcohol, ethyl (4-dimethylaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine, N, N-diethyl-3-phenetidine, tribenzylamine, dibenzylphenylamine, N-methyl-N-phenylbenzylamine, 4-bromo-N, N-dimethylaniline, tridodecylamine, aminophen Luolans (ODB, ODBII, etc.), crystal violet lactone, leuco crystal violet, etc.), acylphosphine oxides (eg bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H -Pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.), JP-A-53-133428, JP 57-1819, 57-6096, and Such as the compounds disclosed in U.S. Patent No. 3,615,455 may also be mentioned.

  Furthermore, the vicinal polyketaldonyl compound disclosed in US Pat. No. 2,367,660, the acyloin ether compound described in US Pat. No. 2,448,828, the α-form described in US Pat. No. 2,722,512 Aromatic acyloin compounds substituted with hydrocarbons, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, organoboron compounds described in JP-A-2002-229194, and other exemplified radicals Generators, phosphonium salt compounds (effective as a cationic polymerization initiator) such as triarylsulfonium salts (salts with hexafluoroantimony or hexafluorophosphate), (phenylthiophenyl) diphenylsulfonium salts, WO01 / 71428 Onium in the publication And compounds can also be used.

  One or two or more photopolymerization initiators can be used in combination. As such a combination, for example, a combination of hexaarylbiimidazole and 4-aminoketone described in US Pat. No. 3,549,367, a benzothiazole compound described in Japanese Patent Publication No. 51-48516, and trihalomethyl-s- Combinations of triazine compounds, combinations of aromatic ketone compounds such as thioxanthone and hydrogen donors (eg dialkylamino-containing compounds, phenol compounds, etc.), combinations of hexaarylbiimidazole and titanocene, coumarins, titanocene and phenylglycines Combination with can also be used.

  The use amount of the photopolymerization initiator is generally in the range of 0.1 to 30% by mass, preferably in the range of 0.5 to 20% by mass with respect to all components of the photosensitive layer in each photosensitive layer. It is particularly preferably in the range of 0.5 to 15% by mass. Further, when adjusting the sensitivity difference of each photosensitive layer by the content of the photopolymerization initiator, the photopolymerization property that the amount of the photopolymerization initiator contained in the second photosensitive layer is contained in the first photosensitive layer. The amount may be larger than the amount of initiator. The content of the photopolymerization initiator in the second photosensitive layer is preferably 1.5 to 100 times the content of the photopolymerization initiator in the first photosensitive layer, and more preferably 1.8 to 50 times. The amount is preferably 2 to 20 times.

[Sensitizer]
A sensitizer can be added for the purpose of adjusting the sensitivity and the photosensitive wavelength in exposure of each photosensitive layer. When using visible light, ultraviolet light or visible light laser as exposure light (active energy rays), the sensitizer is excited by active energy rays, and other substances (for example, radical generators, acid generators, etc.) ) And the like (for example, energy transfer, electron transfer, etc.) to generate a useful group such as a radical or an acid.

  Examples of the sensitizer include known polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, indocarbocyanine, thia). Carbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones ( For example, anthraquinone), squalium (eg, squalium), acridone (eg, acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacrylic) Etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5,7-di-n-propoxycoumarin), 3,3 '-Carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7- Methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7 -Dipropoxycoumarin and the like, and others include JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002- And a coumarin compound described in each publication such as No. 363209).

  As a combination of a polymerization initiator and a sensitizer, for example, an electron transfer type initiator system described in JP-A No. 2001-305734 [(1) an electron donating type initiator and a sensitizing dye, (2) an electron accepting type initiator And sensitizing dyes, (3) electron donating initiators, sensitizing dyes and electron accepting initiators (ternary initiation system)], and the like.

  Each of the first photosensitive layer and the second photosensitive layer may contain a sensitizer. The addition amount of the sensitizer is generally in the range of 0.05 to 30% by mass, preferably in the range of 0.1 to 20% by mass, particularly preferably 0, based on all components of the photosensitive resin composition. The range is from 2 to 10% by mass. When the addition amount of the sensitizer is large, it is deposited from the photosensitive layer during storage, and when it is too small, the sensitivity to the active energy ray is lowered, the exposure process takes time, and the productivity may be lowered.

  When adjusting the sensitivity difference of each photosensitive layer with a sensitizer, if the amount of the sensitizer contained in the second photosensitive layer is larger than the amount of the sensitizer contained in the first photosensitive layer. Good. The content of the sensitizer in the second photosensitive layer is preferably 1.5 to 100 times the amount of the sensitizer in the first photosensitive layer, and more preferably 1.8 to 50 times. Is preferable, and the amount is particularly preferably 2 to 20 times. The first photosensitive layer may be adjusted so as not to contain a sensitizer.

[Other ingredients]
If necessary, the photosensitive layer may be a thermal polymerization inhibitor, a plasticizer, a color former, a colorant, an adhesion promoter for the substrate surface, and other auxiliary agents (for example, pigments, conductive particles, fillers, antifoaming agents). , Flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, thermal cross-linking agents, surface tension modifiers, chain transfer agents, etc.) may be used in combination, thereby stabilizing the intended photosensitive transfer sheet It is possible to adjust properties such as photographic properties, printout properties and film properties. The above-described components can be added to both the first photosensitive layer and the second photosensitive layer, and the addition amount may be determined according to the purpose, and the addition amount to each photosensitive layer is the same or different. Also good.

[Thermal polymerization inhibitor]
A thermal polymerization inhibitor may be added in order to prevent thermal polymerization or polymerization over time of the polymerizable compound in the photosensitive layer. Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-Toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

  The addition amount of the thermal polymerization inhibitor is preferably in the range of 0.001 to 5 mass%, more preferably in the range of 0.005 to 2 mass%, particularly preferably relative to the polymerizable compound of the photosensitive layer. Is in the range of 0.01 to 1% by mass. When the addition amount of the thermal polymerization inhibitor exceeds this range, the sensitivity to active energy rays tends to decrease, and when it exceeds this range, the stability during storage tends to decrease.

[Plasticizer]
A plasticizer may be added to control the film physical properties (flexibility) of the photosensitive layer. Examples of plasticizers include dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diphenyl phthalate, diallyl phthalate, octyl capryl phthalate, etc. Acid esters: triethylene glycol diacetate, tetraethylene glycol diacetate, dimethyl glycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene glycol dicabrylate, etc. Glycol esters; phosphates such as tricresyl phosphate and triphenyl phosphate Ters; Amides such as 4-toluenesulfonamide, benzenesulfonamide, Nn-butylbenzenesulfonamide, Nn-butylacetamide; diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sepacate, dioctyl sepacate , Aliphatic dibasic acid esters such as dioctyl azelate and dibutyl malate; triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, dioctyl 4,5-diepoxycyclohexane-1,2-dicarboxylate And glycols such as polyethylene glycol and polypropylene glycol.

  The addition amount of the plasticizer is preferably in the range of 0.1 to 50% by mass, more preferably in the range of 0.5 to 40% by mass, and particularly preferably 1 to 30% by mass with respect to all components of the photosensitive layer. % Range.

[Coloring agent]
The color former may be added to give a visible image (printing function) to the exposed photosensitive layer. Examples of the color former include tris (4-dimethylaminophenyl) methane (leuco crystal violet), tris (4-diethylaminophenyl) methane, tris (4-dimethylamino-2-methylphenyl) methane, and tris (4-diethylamino). -2-methylphenyl) methane, bis (4-dibutylaminophenyl)-[4- (2-cyanoethyl) methylaminophenyl] methane, bis (4-dimethylaminophenyl) -2-quinolylmethane, tris (4-dipropyl) Aminotriarylmethanes such as aminophenyl) methane; 3,6-bis (dimethylamino) -9-phenylxanthine, 3-amino-6-dimethylamino-2-methyl-9- (2-chlorophenyl) xanthine, etc. Aminoxanthines; 3,6-bis (diethylamino) ) -9- (2-ethoxycarbonylphenyl) thioxanthene, 3,6-bis (dimethylamino) thioxanthene and other aminothioxanthenes; 3,6-bis (diethylamino) -9,10-dihydro-9-phenyl Acridine, amino-9,10-dihydroacridines such as 3,6-bis (benzylamino) -9,10-dihydro-9-methylacridine; aminophenoxazines such as 3,7-bis (diethylamino) phenoxazine Aminophenothiazines such as 3,7-bis (ethylamino) phenothiazone; aminodihydrophenazines such as 3,7-bis (diethylamino) -5-hexyl-5,10-dihydrophenazine; bis (4-dimethylaminophenyl); ) Aminophenylmethanes such as anilinomethane; 4-amino-4'-di Aminohydrocinnamic acids such as methylaminodiphenylamine, 4-amino-α, β-dicyanohydrocinnamic acid methyl ester; hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine; 1,4-bis ( Ethylamino) -2,3-dihydroanthraquinones amino-2,3-dihydroanthraquinones; phenethylanilines such as N, N-diethyl-4-phenethylaniline; 10-acetyl-3,7-bis (dimethylamino) ) An acyl derivative of a leuco dye containing basic NH such as phenothiazine; a leuco-like compound that does not have oxidizable hydrogen such as tris (4-diethylamino-2-tolyl) ethoxycarbonylmentane, but can be oxidized to a coloring compound; Id dyes; U.S. Pat. Nos. 3,042,515 and 3,042,5 Organic amines that can be oxidized to a colored form as described in No. 7 (eg, 4,4′-ethylenediamine, diphenylamine, N, N-dimethylaniline, 4,4′-methylenediamine triphenylamine, N-vinylcarbazole). Particularly preferred are triarylmethane compounds such as leuco crystal violet.

  Furthermore, it is known to combine with a halogen compound for the purpose of coloring these leuco bodies. Examples of halogen compounds are halogenated hydrocarbons (eg carbon tetrabromide, iodoform, ethylene bromide, methylene bromide, amyl bromide, isoamyl bromide, amyl iodide, isobutylene bromide, butyl iodide, diphenyl bromide). Methyl, hexachloroethane, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, 1,2-dibromo-1,1,2-trichloroethane, 1,2,3 tribromopropane, 1-bromo -4-chlorobutane, 1,2,3,4-tetrabromobutane, tetrachlorocyclopropene, hexachlorocyclopentadiene, dibromocyclohexane, 1,1,1-trichloro-2,2-bis (4-chlorophenyl) ethane Halogenated alcohol compounds (for example, 2,2,2-trichloroethanol, tribromoethane, etc.) 1,3-dichloro-2-propanol, 1,1,1-trichloro-2-propanol, di (iodohexamethylene) aminoisopropanol, tribromo-t-butyl alcohol, 2,2,3-trichlorobutane 1,4-diol and the like; halogenated carbonyl compounds (for example, 1,1-dichloroacetone, 1,3-dichloroacetone, hexachloroacetone, hexabromoacetone, 1,1,3,3-tetrachloroacetone, 1,1 , 1-trichloroacetone, 3,4-dibromo-2-butanone, 1,4-dichloro-2-butanone-dibromocyclohexanone, etc.); halogenated ether compounds (eg 2-bromoethyl methyl ether, 2-bromoethyl ethyl ether) , Di (2-bromoethyl) ether, 1,2-dichloroe Halogenated ester compounds (eg, bromoethyl acetate, ethyl trichloroacetate, trichloroethyl trichloroacetate, homopolymers and copolymers of 2,3-dibromopropyl acrylate, trichloroethyl dibromopropionate, α, β-dichloro) Halogenated amide compounds (such as chloroacetamide, bromoacetamide, dichloroacetamide, trichloroacetamide, tribromoacetamide, trichloroethyltrichloroacetamide, 2-bromoisopropionamide, 2,2,2-trichloropropionamide, N-chlorosuccinimide, N-bromosuccinimide, etc.); compounds having sulfur or phosphorus (for example, tribromomethylphenylsulfone, 4-nitrophenyltoxin) Bromomethyl sulfone, 4-chlorophenyl tribromomethyl sulfone, tris (2,3-dibromopropyl) phosphate, etc.), 2,4-bis (such as trichloromethyl) 6-phenyl triazole and the like. Of the organic halogen compounds, a halide having two or more halogen atoms bonded to the same carbon atom is preferable, and a halide having three halogen atoms in one carbon atom is particularly preferable. The organic halogen compounds may be used alone or in combination of two or more. Of these, particularly preferred organic halogen compounds are tribromomethylphenylsulfone and 2,4-bis (trichloromethyl) -6-phenyltriazole.

  The addition amount of the color former is preferably in the range of 0.01 to 20% by mass, more preferably in the range of 0.05 to 10% by mass, and particularly preferably 0.1 to 20% by mass with respect to all the components of the photosensitive layer. It is in the range of 5% by mass. The amount of the halogen compound is generally in the range of 0.001 to 5 mass%, preferably 0.005 to 1 mass%, based on all components of the photosensitive layer.

[dye]
In the photosensitive layer, a dye can be used for the purpose of coloring the photosensitive resin composition for improving handleability or imparting storage stability. Examples of suitable dyes include brilliant green (eg sulfate thereof), eosin, ethyl violet, erythrosine B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymol. Phthalein, Methyl Violet 2B, Quinaldine Red, Rose Bengal, Methanyl-Yellow, Thymolsulfophthalein, Xylenol Blue, Methyl Orange, Orange IV, Diphenyltylocarbazone, 2,7-Dichlorofluorescein, Paramethyl Red, Congo Red , Benzopurpurin 4B, α-naphthyl-red, Nile blue A, phenacetalin, methyl violet, malachite green, parafuchsin, oil blue # 603 (Ori Cement Chemical Industry Co., Ltd.), mention may be made of rhodamine B, and Rotamin 6G, such as Victoria Pure Blue BOH. The counter anion of the cationic dye may be a residue of an organic acid or an inorganic acid. For example, a residue (anion) such as bromic acid, iodic acid, sulfuric acid, phosphoric acid, oxalic acid, methanesulfonic acid, and toluenesulfonic acid. Can be given. Preferred dyes are cationic dyes, such as malachite green oxalate and malachite green sulfate.

  A preferable addition amount of the dye is an amount in the range of 0.001 to 10% by mass with respect to all components of the photosensitive layer. More preferably, it is the range of 0.01-5 mass%, Most preferably, it is the range of 0.1-2 mass%.

[Adhesion promoter]
In order to improve the adhesion between the layers or the adhesion between the photosensitive transfer sheet and the substrate, a known so-called adhesion promoter can be used for each layer.

  As the adhesion promoter, adhesion promoters described in JP-A-5-11439, JP-A-5-341532, and JP-A-6-43638 can be suitably used. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 3-morpholino Methyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, and 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole , Amino group-containing benzotriazole, silane coupling agent and the like.

  A preferable addition amount of the adhesion promoter is in the range of 0.001% by mass to 20% by mass with respect to all components of the photosensitive layer. More preferably, it is the range of 0.01-10 mass%, Most preferably, it is the range of 0.1 mass%-5 mass%.

  The photosensitive layer is, for example, J.I. Contains organic sulfur compounds, peroxides, redox compounds, azo and diazo compounds, photoreducible dyes, and organic halogen compounds as described in Chapter 5 of “Light Sensitive Systems” by Korser Also good. Examples of organic sulfur compounds include di-n-butyl disulfide, dibenzyl disulfide, 2-mercaprobenzthiazole, 2-mercaptobenzoxazole, thiophenol, ethyltrichloromethane sulfenate, and 2-mercaptobenzimidazole. Can be mentioned. Examples of the peroxide include di-t-butyl peroxide, benzoyl peroxide, and methyl ethyl ketone peroxide. The redox compound is a combination of a peroxide and a reducing agent, and examples thereof include ferrous ions and persulfate ions, ferric ions and peroxides. Examples of the azo and diazo compounds include α, α'-azobisiributyronitrile, 2-azobis-2-methylbutyronitrile, and diaminonium of 4-aminodiphenylamine. Examples of the photoreductive dye include rose bengal, erythrosine, eosin, acriflavine, lipoflavin, and thionine.

[Surfactant]
A known surfactant can be added in order to improve the surface unevenness that occurs when manufacturing the photosensitive transfer sheet. Examples of the surfactant can be appropriately selected from anionic and cationic surfactants, nonionic surfactants, amphoteric surfactants, fluorine-containing surfactants, and the like. The addition amount is preferably 0.001 to 10% by mass with respect to the solid content of the photosensitive resin composition, and if it is less than 0.001% by mass, the effect of improving the surface condition cannot be obtained. It is easy to generate a problem of lowering. Fluoroaliphatic group having fluorine chain with hydrogen atoms bonded to at least 3 carbon atoms counted from the non-bonding end as a fluorosurfactant containing 40 mass% or more of carbon atoms with 3 to 20 carbon chains A polymer surfactant having an acrylate or methacrylate having a copolymer as a copolymer component is also preferred.

[Production of photosensitive transfer sheet]
The photosensitive transfer sheet of the present invention can be produced, for example, as follows.
First, the above various materials are dissolved, emulsified or dispersed in water or a solvent to form a first photosensitive resin composition solution for forming a first photosensitive layer and a second photosensitive resin composition for forming a second photosensitive layer. Prepare each solution. Also, a solution for forming the barrier layer is prepared.

  Examples of the solvent for the first photosensitive resin composition solution and the second photosensitive resin composition solution include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, and n-hexanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate Esters; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, monochlorobenzene Ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, and the like. You may mix and use. A known surfactant may be added to the first photosensitive resin composition solution and the second photosensitive resin composition solution.

  As the solvent of the polymer solution for forming the barrier layer, a coating solvent similar to that for the photosensitive layer may be used, or water or a mixed solvent of water and a solvent may be used. As the solvent, the above-mentioned hydrophilic solvents such as alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol can be used. The solvent may be used so that the coating liquid has a solid content of 10% to 90%.

  Next, a 1st photosensitive resin composition solution is apply | coated on a support body, and a 1st photosensitive layer is formed by drying. Next, a coating solution for forming a barrier layer is applied onto the first photosensitive layer and dried. A second photosensitive resin composition solution is applied thereon and dried to form a second photosensitive layer. As described above, the application in the case of multilayering may be sequential coating or simultaneous multilayer coating. The coating method of the photosensitive resin composition solution is not particularly limited. For example, spray method, roll coating method, spin coating method, slit coating method, extrusion coating method, curtain coating method, die coating method, gravure coating method, wire Various methods such as a bar coating method and a knife coating method can be employed. As drying conditions, although it changes also with each component, the kind of solvent, a use ratio, etc., it is about 30 seconds-15 minutes normally at the temperature of 60-110 degreeC.

  Even when there are more photosensitive layers than two layers, a desired photosensitive transfer sheet can be produced by repeating the same operation. By making the photosensitive layer into two or more layers, the total thickness of the photosensitive layers can be in the range of 10 μm to 1 mm.

[Support and protective film]
It is desirable that the support is capable of peeling the photosensitive layer, has good light transmittance, and has good surface smoothness. The support is preferably made of synthetic resin and transparent. Examples of the support include polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly (meth) acrylic acid ester copolymer, polyvinyl chloride, Various plastics such as polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulose film, nylon film, etc. A film can be mentioned. Furthermore, a composite material composed of two or more of these can also be used. Of these, polyethylene terephthalate is particularly preferred. The thickness of the support is preferably 2 to 150 μm, more preferably 5 to 100 μm, and particularly preferably 8 to 50 μm. The support is preferably a long support. The length of the long support used for producing the photosensitive transfer sheet of the present invention may be arbitrarily determined, and for example, a length of 10 m to 20000 m can be used.

  In the photosensitive transfer sheet of the present invention, a protective film can be disposed on the second photosensitive layer. Examples of the protective film include those used for the support and paper or paper laminated with polyethylene or polypropylene. In particular, a polyethylene film and a polypropylene film are preferable. The thickness of the protective film is preferably in the range of 5 to 100 μm, more preferably in the range of 8 to 50 μm, and particularly preferably in the range of 10 to 30 μm. At that time, it is necessary that the adhesive force A between the photosensitive layer and the support and the adhesive force B between the photosensitive layer and the protective film satisfy the relationship of adhesive force A> adhesive force B. Examples of the support / protective film combination include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. Moreover, the above adhesive force relationship can be satisfy | filled by surface-treating at least one of a support body and a protective film. The surface treatment of the support may be performed in order to increase the adhesive strength with the photosensitive layer. For example, coating of an undercoat layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow discharge irradiation treatment , Active plasma irradiation treatment, laser beam irradiation treatment and the like. The coefficient of static friction between the support and the protective film is also important. These static friction coefficients are preferably 0.3 to 1.4, particularly preferably 0.5 to 1.2. If it is less than 0.3, it slips too much, so that when it is made into a roll, a winding deviation occurs. Moreover, when it exceeds 1.4, it will become difficult to wind in a favorable roll shape.

  The photosensitive transfer sheet of the present invention is wound, for example, on a cylindrical core, wound into a roll with a long body, and stored. What is necessary is just to determine the length of this elongate body arbitrarily, for example, what is necessary is just to select in the range of 10 m to 20000 m. The slit may be processed so as to be easy for the user to use, and it may be a long body in the range of 100 m to 1000 m and may be formed into a roll. In this case, it is preferable to wind the support so that the support is on the outermost side. The roll-shaped photosensitive transfer sheet may be slit into a sheet shape. When storing, it is preferable to install a separator (especially moisture-proof and desiccant-containing) on the end surface from the viewpoint of protecting the end surface and preventing edge fusion, and use low moisture-permeable materials for packaging. Is preferred.

  You may surface-treat a protective film. The surface treatment is performed to adjust the adhesion between the protective film and the photosensitive layer. For example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, and polyvinyl alcohol is provided on the surface of the protective film. The undercoat layer is generally formed by applying the polymer coating solution on the surface of the protective film and then drying at 30 to 150 ° C. (especially 50 to 120 ° C.) for 1 to 30 minutes. In addition to the photosensitive layer, barrier layer, support, and protective film, a cushion layer, a release layer, an adhesive layer, a light absorption layer, a surface protective layer, and the like may be included.

[Substrate]
The substrate to which the photosensitive transfer sheet of the present invention is transferred can be arbitrarily selected from those having high surface smoothness to those having an uneven surface. Preferably, a plate-like substrate, a so-called substrate is used. Specific examples include a substrate for producing a known printed wiring board, a glass plate (such as a soda glass plate), a synthetic resin film, paper, and a metal plate.

  The substrate comprises a second photosensitive layer comprising a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator, and a photosensitive resin composition comprising a binder, a polymerizable compound, and a photopolymerization initiator. A photosensitive laminate is formed by laminating a first photosensitive layer exhibiting a light sensitivity relatively lower than that of the second photosensitive layer in this order. Furthermore, it is preferable to form a photosensitive laminate in which a barrier layer is disposed between the first photosensitive layer and the second photosensitive layer.

  The photosensitive transfer sheet of the present invention is widely used as printed wiring boards, color filters, pillar materials, rib materials, spacers, display members such as partition walls, various image forming materials such as holograms, micromachines, and proofs, and pattern forming materials. Is possible. Among these, application to a printed wiring board and a display member is preferable, and application to a printed wiring board is particularly preferable.

[Pattern formation method]
The photosensitive transfer sheet of the present invention comprises (1) a step of obtaining a laminate by laminating the second photosensitive layer on the substrate so as to be on the substrate side, and (2) the first photosensitive layer of the laminate. Irradiating a predetermined image pattern from the side, curing both the first photosensitive layer and the second photosensitive layer in the irradiated region, (3) removing the support from the laminate, and (4) A cured resin formed by curing the first photosensitive layer and the second photosensitive layer on the substrate, including a step of developing the laminate and removing an uncured portion in the laminate. A desired pattern can be formed by a method of forming an image pattern composed of an existing area and an area where no cured resin exists.

  The photosensitive transfer sheet of the present invention includes (1) a step of laminating a second photosensitive layer on a substrate in a positional relationship on the substrate side to obtain a laminate, and (2) a first photosensitive of the laminate. The first of the regions irradiated with light having an image pattern defining a region to be irradiated with light of at least two different levels of irradiation energy amount from the side of the layer, and receiving a relatively large amount of light irradiation energy amount A step of curing both the photosensitive layer and the second photosensitive layer, and curing the second photosensitive layer in a region irradiated with light having a relatively small amount of light irradiation energy; (3) removing the support from the laminate. A resin formed by curing both the first photosensitive layer and the second photosensitive layer on the substrate, including a step and (4) developing the laminate to remove an uncured portion in the laminate. The area where there is, formed by curing the second photosensitive layer Region resin is present which, and by a method for forming an image pattern composed of areas which the cured resin is not present, it is also possible to form a desired pattern.

  However, in the above method, instead of performing the step (3) of removing the support from the laminated body between the step (2) and the step (4), the step (1) and the step (2) You may go between.

  As a light source for light irradiation in the step (2), when light irradiation is performed through a support, an electromagnetic wave that transmits the support and activates a photopolymerization initiator or a sensitizer used, and a wavelength of 300 are used. A light source that generates ultraviolet to visible light in the range of ˜1500 nm, preferably 320 to 800 nm, particularly preferably a light source in the range of 330 nm to 650 nm is used. For example, a known light source such as a (super) high pressure mercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, a fluorescent tube for a copying machine, an LED, a semiconductor laser, or the like can be used. In addition, an electron beam or an X-ray may be used. Even when light irradiation is performed after the support is peeled off, a similar light source can be used. Among these, the light irradiation is preferably performed by laser light irradiation, and the laser wavelength is preferably in the range of 200 to 1500 nm, more preferably in the range of 300 to 800 nm, particularly preferably in the range of 370 nm to 650 nm, and 400 nm to The range of 450 nm is most preferable.

[Method of manufacturing printed wiring board]
The photosensitive transfer sheet of the present invention can be suitably used for the production of a printed wiring board, particularly for the production of a printed wiring board having a hole such as a through hole or a via hole.

  The photosensitive transfer sheet of the present invention comprises (1) a step of obtaining a laminate by laminating the second photosensitive layer on the substrate so as to be on the substrate side, and (2) the first photosensitive layer of the laminate. Irradiating a predetermined wiring pattern from the side, curing both the first photosensitive layer and the second photosensitive layer in the irradiated region, (3) removing the support from the laminate, and (4) The first photosensitive layer and the second photosensitive layer are cured together on the printed wiring board forming substrate, including a step of developing the laminate and removing an uncured portion in the laminate. A desired pattern can be formed by a method of forming a wiring pattern composed of a region covered with the formed cured resin and a region where the substrate surface is exposed.

  The photosensitive transfer sheet of the present invention includes (1) a step of laminating a second photosensitive layer on a substrate in a positional relationship on the substrate side to obtain a laminate, and (2) a first photosensitive of the laminate. From the side of the layer, the hole portion is irradiated with light having a relatively large amount of light irradiation energy to cure both the first photosensitive layer and the second photosensitive layer, and the wiring formation region has a light irradiation energy amount. A step of irradiating an image pattern that cures the second photosensitive layer by applying a relatively small amount of light, (3) a step of removing the support from the laminate, and (4) developing the laminate. And a cured resin formed by curing both the first photosensitive layer and the second photosensitive layer on the printed wiring board forming substrate having a hole portion, including a step of removing an uncured portion in the laminate. Formed by hardening the hole part and the second photosensitive layer covered with Region is coated with the cured resin, and the method of forming the composed wiring pattern and a region where the substrate surface is exposed, it is also possible to form a desired pattern.

  In the above method, instead of performing the step of removing the support from the laminate of (3) between step (2) and step (4), between step (1) and step (2) You may go.

  As the light source for light irradiation in the step (2), a light source similar to the above is used when light is irradiated through the support, which is transmitted through the support. The light source is preferably performed by laser light irradiation.

  Thereafter, in order to obtain a printed wiring board, a method of etching or plating the printed wiring board forming substrate on which the wiring pattern is formed, for example, a known subtractive method or additive method (semi-additive method, full additive method). Method). For the purpose of forming a printed wiring board with industrially advantageous tenting according to the present invention, it is preferable to use a subtractive method by etching. The cured resin remaining on the substrate for forming a printed wiring board after the treatment may be peeled off. In the case of the semi-additive method, the copper thin film portion may be further etched after the peeling, and a desired printed wiring board can be formed. Moreover, a multilayer printed wiring board can also be manufactured similarly to the manufacturing method of the said printed wiring board.

  Next, the manufacturing method of the printed wiring board which has a through hole using the photosensitive transfer sheet of this invention is demonstrated, referring FIG. 7 of an accompanying drawing. FIG. 7 shows a case where the photosensitive transfer sheet shown in FIG. 1 or the photosensitive transfer sheet shown in FIG. 2 is used.

  First, as shown in FIG. 7A, a printed wiring board forming substrate 21 having a through hole 22 and having a surface covered with a metal plating layer 23 is prepared. As the printed wiring board forming substrate 21, a copper-clad laminated substrate and a substrate in which a copper plating layer is formed on an insulating base material such as glass-epoxy, or an interlayer insulating film is laminated on these substrates to form a copper plating layer. A substrate (laminated substrate) can be used.

Next, as shown in FIG. 7B, when the photosensitive transfer sheet 10 has a protective film, the protective film is peeled off, and the second photosensitive layer 14 is a printed wiring board forming substrate 21. The pressure roller 31 is used for pressure bonding so as to be in contact with the surface (laminating step). Thereby, a laminate in which the printed wiring board forming substrate 21, the second photosensitive layer 14, the barrier layer 13, the first photosensitive layer 12, and the support 11 are laminated in this order is obtained. Lamination of the photosensitive transfer sheet can be performed at room temperature (15 to 30 ° C.) or under heating (30 to 180 ° C.). In particular, it is preferable to carry out under heating at 60 to 140 ° C. The roll pressure of the pressure-bonding roll is preferably in the range of 1 to 10 kg / cm ² . The crimping speed is preferably 1 to 3 m / min. Further, the printed wiring board forming substrate 21 may be preheated. Moreover, you may laminate | stack under reduced pressure.

  Instead of using the photosensitive transfer sheet, the second photosensitive resin composition solution, the barrier layer solution, and the first photosensitive resin composition solution for manufacturing the photosensitive transfer sheet are arranged on the surface of the printed wiring board forming substrate in this order. By directly applying and drying, a laminate in which the printed wiring board forming substrate, the second photosensitive layer, the barrier layer, and the first photosensitive layer are laminated in this order can also be obtained.

  Next, as shown in FIG. 7C, the photosensitive layer is cured by irradiating light from the surface of the laminate on the support 11 side. At this time, if necessary (for example, when the light transmittance of the support is insufficient), light irradiation may be performed after the support is peeled off. The wiring pattern forming region of the printed wiring board forming substrate 21 is irradiated with light having a light energy amount necessary for curing the second photosensitive layer 14 in a predetermined pattern, and the wiring pattern forming cured layer 16 is thus formed. Are formed (wiring part exposure step). The opening portion of the through hole 22 of the printed wiring board forming substrate and the periphery thereof are irradiated with light having an amount of light energy necessary for curing the first photosensitive layer 12 and the second photosensitive layer 14, respectively. The region of the hardened layer 17 for protecting the metal layer of the hole is formed (hole part exposure step). The wiring portion exposure step and the hole portion exposure step may be performed independently, but are preferably performed in parallel. The exposure is performed by irradiating light through a photomask, or by irradiating laser light using a laser exposure apparatus. In particular, the latter method using a laser exposure apparatus can be formed without using an expensive mask, which eliminates the process problems caused by the mask, and is suitable for the production of a small variety of products. Yes.

  In the case of irradiating light through a photomask, the amount of light energy for curing only the second photosensitive layer is irradiated through the photomask for forming the region of the hardened layer 16 for wiring pattern formation, and the metal of the through hole It is also possible to use a method in which the exposure is performed twice so as to irradiate a light energy amount for curing both the second photosensitive layer and the first photosensitive layer through a photomask for forming the region of the hardened layer 17 for protecting the layer. Alternatively, the phototransmission created so that the light transmittance corresponding to the region portion of the hardened layer 16 for wiring pattern formation is low and the light transmittance corresponding to the region portion of the hardened layer 17 for protecting the metal layer of the through hole is high. Batch exposure can also be performed using a mask. On the other hand, when irradiating laser light using a laser exposure apparatus, it is preferable to perform scanning exposure while changing the light irradiation amount in each necessary region.

  If the support has not yet been peeled off, the support 11 is peeled off from the laminate as shown in FIG. 7D (support peeling step).

  Next, as shown in FIG. 7E, the uncured regions of the first photosensitive layer 12, the barrier layer 13, and the second photosensitive layer 14 on the printed wiring board forming substrate 21 are dissolved with an appropriate developer. The pattern of the hardened layer 16 for forming the wiring pattern and the hardened layer 17 for protecting the metal layer of the through hole is formed by removing, and the metal plating layer 23 on the substrate surface is exposed (developing step). As the developer, a developer corresponding to the photosensitive resin composition such as an alkaline aqueous solution, an aqueous developer, or an organic solvent may be used. The developer is preferably a weak alkaline aqueous solution. Base components of this 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, potassium phosphate Sodium pyrophosphate, potassium pyrophosphate, borax and the like. The pH of the weak alkaline aqueous solution used for development is preferably about 8 to 12, particularly about 9 to 11. Specifically, 0.1-5 mass% sodium carbonate aqueous solution, potassium carbonate aqueous solution, etc. can be used. The temperature of the developer can be adjusted according to the developability of the photosensitive layer, but is generally preferably about 25 to 40 ° C. In addition, the developer contains a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) and a developing agent. Organic solvents (alcohols, ketones, esters, ethers, amides, lactones, etc.) may be used in combination. As the developer, an aqueous developer obtained by mixing water or an alkaline aqueous solution and an organic solvent may be used, or an organic solvent alone may be used.

  Moreover, you may perform the process which further accelerates | stimulates the hardening reaction of a hardening part by post-heat processing or post-exposure processing as needed after image development. Development may be performed by the wet development method as described above or by a dry development method.

  Next, as shown in FIG. 7F, the metal plating layer 23 exposed on the substrate surface is dissolved and removed with an etching solution (etching step). Since the opening of the through hole 22 is covered with the cured resin composition (tent film) 17, the metal plating of the through hole is performed without the etching solution entering the through hole and corroding the metal plating in the through hole. It will remain in a predetermined shape. Thus, the wiring pattern 24 is formed on the printed wiring board forming substrate 21. When the metal plating layer 23 is made of copper, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, or the like can be used as the etching solution. Among these, a ferric chloride solution is particularly preferable from the viewpoint of etching factor.

  Next, as shown in FIG. 7G, the hardened layers 16 and 17 are removed from the printed wiring board forming substrate as a release piece 18 with a strong alkaline aqueous solution or the like (hardened product removing step). Examples of the basic component of the strong alkaline aqueous solution include sodium hydroxide and potassium hydroxide. The pH of the strong alkaline aqueous solution used is preferably about 12 to 14, particularly about 13 to 14. Specifically, 1-10 mass% sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, etc. can be used.

  The printed wiring board may be a multilayer printed wiring board. Moreover, you may use the photosensitive transfer sheet of this invention not only for said etching process but for a plating process. Examples of plating methods include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, hard gold plating, There are gold plating such as soft gold plating.

[Example 1]
(Formation of first photosensitive layer)
A first photosensitive resin composition solution having the following composition was applied to a 20 μm thick polyethylene terephthalate film and dried to form a 25 μm thick first photosensitive layer.

────────────────────────────────────────
First photosensitive resin composition solution ------------------------------
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymer composition (molar ratio): 55 / 11.7 / 4.5 / 28.8
(Mass average molecular weight: 90,000, Tg: 70 ° C.) 15 parts by mass Adduct of 1/2 mole ratio of hexamethylene diisocyanate and octaethylene oxide mono (meth) acrylate 8 parts by mass 4,4′-bis (diethylamino) benzophenone 04 parts by weight Benzophenone 1.0 part by weight 4-toluenesulfonamide 0.5 part by weight Malachite green oxalate 0.02 part by weight 1,2,4-triazole 0.01 part by weight Leuco Crystal Violet 0.2 part by weight Tri Bromomethylphenylsulfone 0.1 parts by weight Methyl ethyl ketone 30 parts by weight ───────────────────────────────────── ───

(Formation of barrier layer)
On the first photosensitive layer, a water-soluble polymer solution having the following composition was applied and dried to form a barrier layer having a thickness of 1.6 μm.

────────────────────────────────────────
Barrier layer solution ────────────────────────────────────────
Polyvinyl alcohol derivative represented by the following structural formula 13 parts by weight Polyvinylpyrrolidone 6 parts by weight Water 200 parts by weight Methanol 180 parts by weight ───────────────────────── ───────────────

Polyvinyl alcohol derivative (polymerization group introduction rate is 2 mol%)

(Formation of second photosensitive layer)
On the barrier layer, a second photosensitive resin composition solution having the following composition was applied and dried to form a second photosensitive layer having a thickness of 5 μm.

────────────────────────────────────────
Second photosensitive resin composition solution ────────────────────────────────────────
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymer composition (molar ratio): 40 / 26.7 / 4.5 / 28.8, mass average molecular weight: 90,000, Tg: 50 ° C.) 15 parts by mass Polypropylene glycol diacrylate 6.5 parts by mass Tetraethylene glycol dimethacrylate 1.5 parts by mass 4,4′-bis (diethylamino) benzophenone 0.4 parts by mass Benzophenone 3.0 parts by mass 4- Toluenesulfonamide 0.5 part by weight Malachite green oxalate 0.02 part by weight 1,2,4-triazole 0.01 part by weight Leuco Crystal Violet 0.2 part by weight Tribromomethylphenylsulfone 0.1 part by weight Methyl ethyl ketone 10 Parts by mass 1-methoxy-2-propa Lumpur 20 parts by ────────────────────────────────────────

(Preparation of photosensitive transfer sheet)
Finally, a 12 μm thick polypropylene film was laminated on the second photosensitive layer to obtain a photosensitive transfer sheet. In all the layers, the film thickness unevenness was within ± 5%. As a result of measuring the sensitivity of the photosensitive transfer sheet thus obtained by the method described later, the shortest development time is 30 seconds, the amount of light energy A required to cure the second photosensitive layer is 4 mJ / cm ² , The amount of light energy B required to cure one photosensitive layer is 40 mJ / cm ² , and the amount of light energy C required for the first photosensitive layer to cure is 14 mJ / cm ² (light energy amount C and light The ratio C / A with the energy amount A was 3.5, and the ratio A / B between the light energy amount A and the light energy amount B was 0.1). When the photosensitivity of the first photosensitive layer was 1, the photosensitivity of the second photosensitive layer was 10.

[Example 2]
(Synthesis example of polyvinyl alcohol derivative)
10 parts by mass of polyvinyl alcohol (PVA205 Kuraray Co., Ltd.) is dissolved in 90 parts by mass of water. A solution prepared by dissolving 2.3 parts by mass of methylolacrylamide in 20.7 parts by mass of water and 0.002 parts by mass of hydroquinone are added. To this, 0.04 part by mass of sulfuric acid was added and reacted at 40 ° C. for 4 hours to obtain a 10% by mass aqueous solution of polyvinyl alcohol having an acrylamide group in the side chain.

(Preparation of photosensitive transfer sheet)
A photosensitive transfer sheet was obtained in the same manner as in Example 1 except that the barrier layer solution in Example 1 was changed to the following.

────────────────────────────────────────
Barrier layer solution ────────────────────────────────────────
10% aqueous solution of synthesized polyvinyl alcohol derivative 130 parts by weight Polyvinylpyrrolidone 6 parts by weight Water 83 parts by weight Methanol 180 parts by weight ───────────────────────── ───────────────

In all the layers, the film thickness unevenness was within ± 5%. As a result of measuring the sensitivity of the photosensitive transfer sheet thus obtained by the method described later, the shortest development time is 30 seconds, the amount of light energy A required to cure the second photosensitive layer is 4 mJ / cm ² , The amount of light energy B required to cure one photosensitive layer is 40 mJ / cm ² , and the amount of light energy C required for the first photosensitive layer to cure is 14 mJ / cm ² (light energy amount C and light The ratio C / A with the energy amount A was 3.5, and the ratio A / B between the light energy amount A and the light energy amount B was 0.1).

[Example 3]
(Preparation of photosensitive transfer sheet)
A photosensitive transfer sheet was obtained in the same manner as in Example 1 except that the barrier layer solution in Example 1 was changed to the following.

────────────────────────────────────────
Barrier layer solution ────────────────────────────────────────
Polyvinyl alcohol (PVA205, Kuraray Co., Ltd.) 13 parts by weight Polyvinylpyrrolidone 3 parts by weight Nonapropylene glycol diacrylate 3 parts by weight Water 200 parts by weight Methanol 180 parts by weight ─────────────── ─────────────────────────

In all the layers, the film thickness unevenness was within ± 5%. As a result of measuring the sensitivity of the photosensitive transfer sheet thus obtained by the method described later, the shortest development time is 30 seconds, the amount of light energy A required to cure the second photosensitive layer is 4 mJ / cm ² , The amount of light energy B required to cure one photosensitive layer is 40 mJ / cm ² , and the amount of light energy C required for the first photosensitive layer to cure is 14 mJ / cm ² (light energy amount C and light The ratio C / A with the energy amount A was 3.5, and the ratio A / B between the light energy amount A and the light energy amount B was 0.1). When the photosensitivity of the first photosensitive layer was 1, the photosensitivity of the second photosensitive layer was 10.

[Comparative Example 1]
A photosensitive transfer sheet was prepared in the same manner as in Example 1 except that the film thickness of the first photosensitive layer in Example 1 was changed to 30 μm and the barrier layer and the second photosensitive layer were not applied. As a result of measuring the sensitivity of the photosensitive transfer sheet thus obtained by the method described later, the shortest development time was 25 seconds, and the amount of light energy B required to cure the photosensitive layer was 40 mJ / cm ^2. The amount of light energy C required until the curing of was started was 14 mJ / cm ² .

[Comparative Example 2]
The first photosensitive layer and the barrier layer in Example 1 were not applied, and a photosensitive transfer sheet consisting of only a second photosensitive layer having a thickness of 5 μm was prepared. The sensitivity of the photosensitive transfer sheet thus obtained was measured by the method described below. As a result, the shortest development time was 10 seconds or less, and the amount of light energy B required to cure the second photosensitive layer was 4 mJ / cm ² .

[Measurement method of sensitivity]
(1) Measuring method of shortest development time The second photosensitive layer of the photosensitive transfer sheet while peeling the protective film of the photosensitive transfer sheet on the surface of the copper-clad laminate (without through holes) polished, washed and dried. The photosensitive transfer sheet is pressure-bonded using a laminator (MODEL8B-720-PH, manufactured by Taisei Laminator Co., Ltd.) so as to be in contact with the substrate, and a copper-clad laminate, a second photosensitive layer, a barrier layer, and a first photosensitive layer Then, a laminate in which polyethylene terephthalate films are laminated in this order is produced. The pressure bonding conditions were a pressure roll temperature of 105 ° C., a pressure roll pressure of 3 kg / cm ² , and a pressure bonding speed of 1 m / min. The polyethylene terephthalate film is peeled off from the laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. is sprayed on the entire surface of the photosensitive layer on the copper clad laminate at a pressure of 0.15 MPa. The time required from the start of spraying of the aqueous sodium carbonate solution until the photosensitive layer on the copper clad laminate is dissolved and removed is measured, and this is taken as the shortest development time.

(2) Measurement of sensitivity A photosensitive transfer sheet is laminated on a substrate in the same manner as the measurement of the shortest development time. The photosensitive transfer sheet photosensitive layer, using an exposure apparatus having a 405nm laser source from polyethylene terephthalate film side, different amount of light energy to 100 mJ / cm ² at 2 ^1/2 times the interval from 0.1 mJ / cm ² Irradiate light to cure the photosensitive layer. After leaving still at room temperature for 10 minutes, a polyethylene terephthalate film is peeled off from a laminated body. On the entire surface of the resin composition layer on the copper clad laminate, a 1% by mass aqueous sodium carbonate solution at 30 ° C. was sprayed at a spray pressure of 0.15 MPa for a time twice as long as the shortest development time obtained in (1) above. The cured resin composition is dissolved and removed, and the thickness of the remaining cured layer is measured. Next, a sensitivity curve is obtained by plotting the relationship between the light irradiation amount and the thickness of the cured layer. From the sensitivity curve thus obtained, the amount of light energy (light energy amount A) when the thickness of the cured layer is 5 μm, the amount of light energy (light energy amount B) when the thickness of the cured layer is 31.6 μm. ), And the amount of light energy (light energy amount C) when the thickness of the cured layer exceeds 5 μm.

[Measurement method of resolution]
Under the same conditions as the evaluation method for the shortest development time in (1) above, a laminate in which a copper clad laminate, a second photosensitive layer, a barrier layer, a first photosensitive layer, and a polyethylene terephthalate film were laminated in this order was prepared. And let stand at room temperature (23 ° C., 55% RH) for 10 minutes. From the obtained polyethylene terephthalate film of the laminate, an exposure apparatus having a laser light source of 405 nm is used to expose each line width in 5 μm increments from 10 μm to 50 μm in line width / space = 1/1. The exposure amount at this time is the amount of light energy that cures the second photosensitive layer of each photosensitive transfer sheet. After leaving still at room temperature for 10 minutes, a polyethylene terephthalate film is peeled off from a laminated body. An uncured resin is sprayed on the entire surface of the resin composition layer on the copper-clad laminate by spraying a 1% by mass sodium carbonate aqueous solution at 30 ° C. at a spray pressure of 0.15 MPa for twice the shortest development time obtained above. Dissolve the composition. The surface of the copper-clad laminate with the cured resin pattern thus obtained was observed with an optical microscope, and the minimum line width without any abnormalities such as tsumari and twisting was measured on the cured resin pattern line. To do. The smaller the numerical value, the better the resolution.

[Manufacture and evaluation of printed wiring boards]
Photosensitivity with a protective film peeled off on a copper-clad laminate that has 200 through-holes each with a diameter of 3mm and 0.2mm, with a copper plating layer on the inner wall, and whose surface has been polished, washed and dried. The second photosensitive layer of the transfer sheet is stacked and laminated, and a laminate in which a copper-clad laminate, a second photosensitive layer, a barrier layer, a first photosensitive layer, and a polyethylene terephthalate film are laminated in this order in the same manner as described above. Prepare and leave at room temperature (23 ° C., 55% RH) for 10 minutes. Light from which the second photosensitive layer of each photosensitive transfer sheet is cured on the wiring pattern formation region of the copper-clad laminate using an exposure device having a laser light source of 405 nm from above the polyethylene terephthalate film of the obtained laminate. Light with an energy amount is irradiated in a predetermined pattern, while light with an amount of light energy that cures the first photosensitive layer of each photosensitive transfer sheet is applied to the opening of the through hole of the copper clad laminate and the surrounding area. Irradiated to expose the photosensitive layer. After the exposure, the polyethylene terephthalate film is peeled off from the laminate, and then the aqueous solution of sodium carbonate is sprayed on the surface of the photosensitive layer in the same manner as in the evaluation method described above, so that the uncured areas of the first photosensitive layer, the barrier layer and the second photosensitive layer are removed. It was dissolved and removed to obtain a cured layer relief (only the second photosensitive layer was cured in the wiring pattern portion, and the first photosensitive layer, the barrier layer, and the second photosensitive layer were cured in the opening portion of the through hole and the surrounding area). The obtained cured layer pattern was observed with a microscope, and the number of tent film tears (tent properties) of the cured layer on the through-hole openings having a diameter of 3 mm and a diameter of 0.2 mm was observed.
In addition, when the thickness of the hardened layer at this time was measured with a laser microscope (VK-9500, manufactured by Keyence Corporation), the thickness of the hardened layer on the wiring pattern formation region was 5 μm, and it was on the through hole opening. The thickness of the hardened layer was 31.2 μm (30 μm in Comparative Example 1).

  Next, an iron chloride etchant (ferric chloride-containing etching solution) is sprayed on the surface of the copper-clad laminate to dissolve and remove the exposed copper layer not covered with the hardened layer. Next, a 2% by mass sodium hydroxide aqueous solution is sprayed to remove the cured product relief, thereby obtaining a printed wiring board having through holes and having a wiring pattern-like copper layer on the surface. The presence or absence of abnormality of the copper plating layer (whether or not copper plating remains) on the inner wall of the through hole of the obtained printed wiring board was visually observed.

[Evaluation of storage stability]
The photosensitive transfer sheet is stored for one day in an environment of 40 ° C. and 60% RH. Thereafter, the same evaluation as the above-described sensitivity measurement method was performed. As a result, it is possible to form patterns with different thicknesses of the cured film, that is, a portion where only the second photosensitive layer is cured according to the exposure amount and a portion where both the first photosensitive layer / the second photosensitive layer are cured according to the exposure amount. Good, and those in which such pattern formation is impossible (sensitivity difference between photosensitive layers is reduced or sensitivity difference is eliminated) were evaluated as defective.

  Table 1 shows the results of evaluating the resolution, tent tear (diameter 3 mm and 0.2 mm), presence or absence of copper plating in the through hole, and storage stability of the photosensitive transfer sheet thus obtained. Show.

Table 1 ─────────────────────────────────────────
Photosensitive transfer Resolution tent tearing Inside through-hole Storage stability sheet 3mm 0.2mm Copper plating abnormality ───────────────────────────── ───────────
Example 1 20 μm None None None Good Example 2 20 μm None None None Good Example 3 20 μm None None None Good ────────────────────────── ──────────────
Comparative Example 1 40 μm None None None ―
Comparative Example 2 20 μm All torn All torn
────────────────────────────────────────
(註)
―: Not evaluated because it does not have photosensitive layers with different sensitivities

[Example 4]
(Formation of first photosensitive layer)
A 20 μm thick polyethylene terephthalate film was coated with a first photosensitive resin composition solution having the following composition and dried to form a 20 μm thick first photosensitive layer.

────────────────────────────────────────
First photosensitive resin composition solution ------------------------------
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymer composition (molar ratio): 55 / 11.7 / 4.5 / 28.8, mass average molecular weight: 90,000, Tg: 70 ° C.) 15 parts by mass Dodeca polypropylene glycol diacrylate 6.5 parts by mass Tetraethylene glycol dimethacrylate 1.5 parts by mass 4,4′-bis (diethylamino) benzophenone 0.04 parts by mass Benzophenone 1.0 parts by mass 4 -Toluenesulfonamide 0.5 part by weight Malachite green oxalate 0.02 part by weight 1,2,4-triazole 0.01 part by weight Leuco Crystal Violet 0.2 part by weight Tribromomethylphenylsulfone 0.1 part by weight Methyl ethyl ketone 30 parts by mass ───────── ───────────────────────────────

(Formation of barrier layer)
On the first photosensitive layer, a water-soluble polymer solution having the following composition was applied and dried to form a 1.6 μm thick barrier layer.

────────────────────────────────────────
Water-soluble polymer solution ────────────────────────────────────────
Polyvinyl alcohol derivative represented by the following structural formula 13 parts by weight Polyvinylpyrrolidone 6 parts by weight Water 200 parts by weight Methanol 180 parts by weight ───────────────────────── ───────────────

Polyvinyl alcohol derivative

(Formation of second photosensitive layer)
On the barrier layer, a second photosensitive resin composition solution having the following composition was applied and dried to form a second photosensitive layer having a thickness of 10 μm.

────────────────────────────────────────
Second photosensitive resin composition solution
────────────────────────────────────────
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymer composition (molar ratio): 55 / 11.7 / 4.5 / 28.8
(Mass average molecular weight: 90,000, Tg: 70 ° C.) 24 parts by mass A 1/2 molar ratio adduct of hexamethylene diisocyanate and octaethylene oxide mono (meth) acrylate 12 parts by mass N-methylacridone 0.2 parts by mass 2, 2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole 0.8 part by mass 2-mercaptobenzimidazole 0.2 part by mass 4-toluenesulfonamide 0.8 part by mass Malachite Green oxalate 0.03 parts by mass 1,2,4-triazole 0.03 parts by mass Leuco Crystal Violet 0.32 parts by mass Tribromomethylphenylsulfone 0.25 parts by mass Methyl ethyl ketone 55 parts by mass 1-methoxy-2-propanol 8 Mass part ─────────────────────── ────────────────

(Formation of barrier layer)
On the second photosensitive layer, a water-soluble polymer solution having the above composition was applied and dried to form a 1.6 μm thick barrier layer.

(Formation of third photosensitive layer)
On the barrier layer, a third photosensitive resin composition solution having the following composition was applied and dried to form a third photosensitive layer having a thickness of 5 μm.

────────────────────────────────────────
Third photosensitive resin composition solution ------------------------------
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymer composition (molar ratio): 40 / 26.7 / 4.5 / 28.8, mass average molecular weight: 90,000, Tg: 50 ° C.) 13 parts by mass dodeca polypropylene glycol diacrylate 8.1 parts by mass tetraethylene glycol dimethacrylate 1.9 parts by mass N-methylacridone 0.16 parts by mass 2,2′-bis (2-chlorophenyl)- 4,4 ′, 5,5′-tetraphenylbiimidazole 1.04 parts by mass 4-toluenesulfonamide 0.5 parts by mass Malachite green oxalate 0.02 parts by mass 1,2,4-triazole 0.01 parts by mass Parts Leuco Crystal Violet 0.2 parts by mass Tribromomethylphenylsulfone 0.1 parts by mass 10 parts by mass of butyl ethyl ketone 20 parts by mass of 1-methoxy-2-propanol ─────────────────────────── ──────

(Preparation of photosensitive transfer sheet)
A 12 μm-thick polypropylene film (protective film) was laminated on the third photosensitive layer to obtain a photosensitive transfer sheet. In all the layers, the film thickness unevenness was within ± 5%. As a result of measuring the sensitivity of the photosensitive transfer sheet thus obtained in the same manner as described above, the amount of light energy required for curing the third photosensitive layer was 1 mJ / cm ² , and the second photosensitive layer was cured. The amount of light energy required for this is 8 mJ / cm ² , and the amount of light energy required until curing of the second photosensitive layer is 3 mJ / cm ² , and the light necessary for curing the first photosensitive layer. The amount of energy was 35 mJ / cm ² , and the amount of light energy required until the first photosensitive layer was cured was 14 mJ / cm ² . C / A = 8/3 and A / B = 3/14 between the third photosensitive layer and the second photosensitive layer, and C / A = between the second photosensitive layer and the first photosensitive layer. It was 1.75 and A / B = 8/35.

  A copper-clad laminate, a third photosensitive layer, a barrier layer, a second photosensitive layer, a barrier layer, a first photosensitive layer, and a polyethylene terephthalate film were laminated in this order under the same conditions as the evaluation method for the shortest development time. A laminate is prepared and allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes. Pattern irradiation was performed while changing the exposure amount from above the obtained polyethylene terephthalate film of the laminate using an exposure apparatus having a 405 nm laser light source. Thereafter, the polyethylene terephthalate film was peeled off and developed in the same manner as in Example 1. As a result, the portion irradiated with the low energy amount as shown in FIG. 10 has a thickness of 5 μm, the portion irradiated with the medium energy amount is 16.6 μm, and the portion irradiated with the high energy amount is different from the thickness 38.2 μm. A pattern was formed.

It is a schematic cross section of an example of the photosensitive transfer sheet according to the present invention. It is a schematic cross section of the other example of the photosensitive transfer sheet according to the present invention. It is a graph which shows the sensitivity curve showing the relationship between the irradiation amount of light, and the thickness of a hardening layer when light is irradiated to the photosensitive transfer sheet of this invention from the support body side. It is a schematic cross section of an example of the photosensitive transfer sheet according to the present invention. It is a schematic cross section of the other example of the photosensitive transfer sheet according to the present invention. It is a schematic diagram which shows the example of an image (hardened layer pattern) which can be formed using the photosensitive transfer sheet whose photosensitive layer according to this invention is three layers. It is process drawing which shows the manufacturing process of the printed wiring board which has a through hole according to this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Photosensitive transfer sheet 11 Support body 12 1st photosensitive layer 13 Barrier layer 14 2nd photosensitive layer 15 Protective film 16 Hardening layer for wiring pattern formation 17 Hardening layer for metal layer protection 18 Peeling piece 21 Printed wiring board formation board 22 Through Hole 23 Metal plating layer 24 Wiring pattern 31 Pressure roller 50 Photosensitive transfer sheet 51 Support body 52 First photosensitive layer 53 Barrier layer 54 Second photosensitive layer 55 Third photosensitive layer 56 Protective film 57 Substrate

Claims (38)

  From the photosensitivity of the first photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator on the support, a barrier layer containing the polymerizable compound, a binder, a polymerizable compound and a photopolymerization initiator. A photosensitive transfer sheet in which second photosensitive layers having relatively high photosensitivity are laminated in this order.   The photosensitive transfer sheet according to claim 1, wherein the barrier layer has photosensitivity, and the photosensitivity of the barrier layer is relatively lower than the photosensitivity of the first photosensitive layer.   The photosensitive transfer sheet according to claim 1, wherein the polymerizable compound contained in the barrier layer is a polymer having a polymerizable group.   The photosensitive transfer sheet according to claim 3, wherein the polymer having a polymerizable group has an affinity for water or a lower alcohol having 1 to 4 carbon atoms.   The photosensitivity according to claim 4, wherein the polymer having a polymerizable group having an affinity for water or a lower alcohol having 1 to 4 carbon atoms is soluble in water or a lower alcohol having 1 to 4 carbon atoms. Transfer sheet.   The photosensitive transfer sheet according to claim 1, wherein the barrier layer further comprises a polymer having an affinity for water or a lower alcohol having 1 to 4 carbon atoms.   The photosensitive transfer sheet according to claim 6, wherein the polymer having affinity for water or a lower alcohol having 1 to 4 carbon atoms is soluble in water or a lower alcohol having 1 to 4 carbon atoms.   The photosensitive transfer sheet according to claim 1, wherein the barrier layer has a thickness in the range of 0.1 to 5 μm.   The photosensitive transfer sheet according to any one of claims 1 to 8, wherein the photosensitivity of the first photosensitive layer is 1 and the photosensitivity of the second photosensitive layer is in the range of 2 to 200.   The ratio expressed by A / B between the amount of light energy A required to cure the second photosensitive layer and the amount of light energy B necessary to cure the first photosensitive layer is 0.005 to 0.5. The photosensitive transfer sheet according to any one of claims 1 to 9, which is in the range of.     The ratio represented by C / A between the amount of light energy A required to cure the second photosensitive layer and the amount of light energy C required until the first photosensitive layer begins to be cured is in the range of 1-10. The photosensitive transfer sheet according to any one of claims 1 to 10.   The amount of photopolymerization initiator contained in the second photosensitive layer is larger than the amount of photopolymerization initiator contained in the first photosensitive layer. Transfer sheet.   The photosensitive transfer according to any one of claims 1 to 12, wherein the amount of the polymerizable compound contained in the second photosensitive layer is larger than the amount of the polymerizable compound contained in the first photosensitive layer. Sheet.   The photosensitive transfer sheet according to claim 1, wherein the first photosensitive layer has a thickness in the range of 1 to 100 μm, and the thickness is larger than the thickness of the second photosensitive layer.   The photosensitive transfer sheet according to claim 1, wherein the second photosensitive layer has a thickness in the range of 0.1 to 15 μm.   The photosensitive transfer sheet according to any one of claims 1 to 15, wherein the support is made of a synthetic resin and is transparent.   The photosensitive transfer sheet according to any one of claims 1 to 16, wherein the support is a long support.   The photosensitive transfer sheet according to any one of claims 1 to 17, wherein a protective film is disposed on the second photosensitive layer.   The photosensitive transfer sheet according to any one of claims 1 to 18, which is a long body and is wound in a roll shape.   The photosensitive transfer sheet according to any one of claims 1 to 19, which is used for producing a printed wiring board.   On the substrate, a second photosensitive layer containing a binder, a polymerizable compound and a photopolymerization initiator, a barrier layer containing a polymerizable compound, a binder, a polymerizable compound and a photopolymerization initiator containing a photosensitivity than the second photosensitive layer. A photosensitive laminate in which first photosensitive layers having relatively low photosensitivity are laminated in this order.   The photosensitive laminate according to claim 21, wherein the barrier layer has photosensitivity, and the photosensitivity of the barrier layer is relatively lower than the photosensitivity of the first photosensitive layer.   The photosensitive laminate according to claim 21, wherein the polymerizable compound contained in the barrier layer is a polymer having a polymerizable group.   The photosensitive laminate according to claim 23, wherein the polymer having a polymerizable group has an affinity for water or a lower alcohol having 1 to 4 carbon atoms.   The polymer according to claim 24, wherein the polymer has a polymerizable group having an affinity for water or a lower alcohol having 1 to 4 carbon atoms, and is soluble in water or a lower alcohol having 1 to 4 carbon atoms. Photosensitive laminate.   The photosensitive laminate according to claim 21, wherein the barrier layer further comprises a polymer having an affinity for water or a lower alcohol having 1 to 4 carbon atoms.   27. The photosensitive laminate according to claim 26, wherein the polymer having an affinity for water or a lower alcohol having 1 to 4 carbon atoms is soluble in water or a lower alcohol having 1 to 4 carbon atoms.   28. The photosensitive laminate according to any one of claims 21 to 27, wherein the barrier layer has a thickness in the range of 0.1 to 5 [mu] m.   The photosensitive laminate according to any one of claims 21 to 28, wherein the substrate is a printed wiring board forming substrate.   30. The photosensitive laminate according to any one of claims 21 and 29, wherein a support is laminated on the first photosensitive layer. An image comprising a region where a cured resin layer formed by curing both the first photosensitive layer and the second photosensitive layer on a substrate and a region where no cured resin layer is present, including the following steps: How to form a pattern:
(1) A step of laminating the photosensitive transfer sheet according to claim 1 on a substrate in a positional relationship such that the second photosensitive layer is on the substrate side;
(2) A step of performing light irradiation of a predetermined image pattern from the side of the first photosensitive layer of the laminate and curing both the first photosensitive layer and the second photosensitive layer in the region irradiated with the light;
(3) removing the support from the laminate; and
(4) The process of developing a laminated body and removing the unhardened part in a laminated body. A region including a resin layer formed by curing the first photosensitive layer and the second photosensitive layer on the substrate, including the following steps: a resin layer formed by curing the second photosensitive layer A method of forming an image pattern composed of a region in which a cured resin layer does not exist:
(1) A step of laminating the photosensitive transfer sheet according to claim 1 on a substrate in a positional relationship such that the second photosensitive layer is on the substrate side;
(2) Light irradiation is performed from the first photosensitive layer side of the laminate with an image pattern that defines a region to be irradiated with at least two different levels of irradiation energy amount, and the light irradiation energy amount is relatively large Curing both the first photosensitive layer and the second photosensitive layer in the region irradiated with light, and curing the second photosensitive layer in the region irradiated with light having a relatively small amount of light irradiation energy;
(3) removing the support from the laminate; and
(4) The process of developing a laminated body and removing the unhardened part in a laminated body.   32. The step of removing the support from the laminate of (3) is performed between step (1) and step (2) instead of between step (2) and step (4). 33. The method according to 32.   The method according to any one of claims 31 to 33, wherein the light irradiation in the step (2) is performed by laser light irradiation. The area covered with the cured resin layer formed by curing the first photosensitive layer and the second photosensitive layer on the printed wiring board forming substrate including the following steps and the substrate surface are exposed. A method of forming a wiring pattern composed of a region including:
(1) A step of laminating the photosensitive transfer sheet according to claim 1 on a substrate in a positional relationship such that the second photosensitive layer is on the substrate side;
(2) A step of irradiating a predetermined wiring pattern from the first photosensitive layer side of the laminate and curing both the first photosensitive layer and the second photosensitive layer in the irradiated region;
(3) removing the support from the laminate; and
(4) The process of developing a laminated body and removing the unhardened part in a laminated body. A hole part covered with a cured resin layer formed by curing both the first photosensitive layer and the second photosensitive layer on a printed wiring board forming substrate having a hole part, including the following steps: A method of forming a wiring pattern composed of a region covered with a cured resin layer formed by curing a photosensitive layer and a region where a substrate surface is exposed:
(1) A step of laminating the photosensitive transfer sheet according to claim 1 on a substrate in a positional relationship such that the second photosensitive layer is on the substrate side;
(2) From the side of the first photosensitive layer of the laminate, the hole portion is irradiated with light having a relatively large amount of light irradiation energy to cure both the first photosensitive layer and the second photosensitive layer, and wiring A step of irradiating the formation region with light of an image pattern that cures the second photosensitive layer by applying light irradiation with a relatively small amount of light irradiation energy;
(3) removing the support from the laminate; and
(4) The process of developing a laminated body and removing the unhardened part in a laminated body.   36. The step (3) of removing the support from the laminated body is performed between the step (1) and the step (2) instead of between the step (2) and the step (4). 36. The method according to 36.   The method according to any one of claims 35 to 37, wherein the light irradiation in the step (2) is performed by laser light irradiation.

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