KR20060041783A - Photosensitive transfer sheet, photosensitive laminate, image pattern forming method, and wiring pattern forming method - Google Patents

Abstract

(Problem) Provided are a photosensitive transfer sheet and a photosensitive laminate which can easily form desired patterns having different thicknesses in an image.

(Solution means) A first photosensitive layer comprising a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator on a support, and a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator, and the first The photosensitive transfer sheet | seat in which the 2nd photosensitive layer which shows the light sensitivity comparatively higher than the photosensitivity of the photosensitive layer is laminated | stacked in this order, and at least one binder of a 1st photosensitive layer and a 2nd photosensitive layer is a polyurethane resin. On the photosensitive laminate, the second photosensitive layer and the first photosensitive layer are sequentially stacked on a substrate.

Description

PHOTOSENSITIVE TRANSFER SHEET, PHOTOSENSITIVE LAMINATE, IMAGE PATTERN FORMING METHOD, AND WIRING PATTERN FORMING METHOD}

1 is a schematic sectional view of an example of a photosensitive transfer sheet according to the present invention.

2 is a schematic sectional view of another example of the photosensitive transfer sheet according to the present invention.

3 is a schematic sectional view of another example of the photosensitive transfer sheet according to the present invention.

4 is a schematic sectional view of another example of the photosensitive transfer sheet according to the present invention.

Fig. 5 is a graph showing a sensitivity curve showing the relationship between the dose of light and the thickness of the cured layer when the photosensitive transfer sheet of the present invention is irradiated with light from the support side.

6 is a schematic sectional view of an example of the photosensitive transfer sheet according to the present invention.

7 is a schematic sectional view of another example of the photosensitive transfer sheet according to the present invention.

8 is a schematic sectional view of another example of the photosensitive transfer sheet according to the present invention.

9 is a schematic sectional view of another example of the photosensitive transfer sheet according to the present invention.

Fig. 10 is a schematic diagram showing an example of an image (cured layer pattern) which can be formed using a photosensitive transfer sheet having three photosensitive layers according to the present invention.

11 is a process chart showing a manufacturing process of a printed wiring board having a through hole according to the present invention.

(Short description of drawing symbols)

10 Photosensitive Transfer Sheet 11 Support

12 First photosensitive layer 13 Barrier layer

14 2nd photosensitive layer 15 protective film

16 Hardened layer for wiring pattern formation 17 Hardened layer for metal layer protection of through hole

18 Peeling board 21 Board for forming printed wiring board

22 Through Hole 23 Metal Plating Layer

24 Wiring Pattern 31 Pressure Roller

50 Photosensitive Transfer Sheet 51 Support

52 First Photosensitive Layer 53 Barrier Layer

54 Second Photosensitive Layer 55 Third Photosensitive Layer

56 protective film 57 substrate

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 particularly relates to a photosensitive transfer sheet, a laminate, and a method of forming a wiring pattern of a printed wiring board using the photosensitive transfer sheet or the laminate, which are useful for manufacturing a printed wiring board.

The photosensitive transfer sheet having a support and a photosensitive layer is used for manufacturing various types of image forming materials such as printed wiring boards, color filters, aggregate materials, rib members, spacers, display members such as partitions, printing plates, holograms, micromachines, and proofs. It is widely used as an image type pattern forming material.

In the manufacturing field of a printed wiring board, a wiring pattern is formed by the photolithography technique which used the photosensitive transfer sheet (also called dry film resist) which consists of a transparent support body (for example, polyethylene terephthalate) and the photosensitive layer formed on the support body. Forming is done. For example, in the manufacture of a printed wiring board having a through hole, a through hole is formed in a substrate for forming a printed wiring board (for example, a copper-clad laminate), and a metal plating layer is formed in the side wall portion of the through hole. The photosensitive layer of the photosensitive transfer sheet is overlaid on the surface of the substrate to be brought into close contact with each other, and light is irradiated onto each of the regions including the wiring pattern forming region and the through hole opening in a predetermined pattern to cure the photosensitive layer. Subsequently, the support of the photosensitive transfer sheet was peeled off, and the uncured region other than the cured region on the wiring pattern forming region and the cured region on the through hole opening region (referred to as a tent film) was dissolved and removed using a developer, followed by the exposed metal layer portion. Etching is performed and then the hardened region is removed, thereby producing a wiring pattern on the substrate surface.

The method of protecting the metal plated layer of the through hole using the above tent film is generally called a tenting method. Moreover, in the printed wiring board of a multilayer structure, the hole for interlayer connection called a via hole may be provided, and also in this case, it is necessary to protect a via hole part with a tent film | membrane at the time of wiring pattern formation similarly.

In recent years, the demand for higher density of printed wiring boards is increasing, and a photoresist film capable of higher resolution is required. In order to raise the resolution of a photoresist film, it is effective to make the film thickness of the photosensitive layer thin. However, as mentioned above, the hardened layer hardened | cured by the photosensitive layer also serves to protect the through-hole or via hole formed in the printed wiring board, and when the film thickness of a photosensitive layer is simply thinned, the uncured area | region of the photosensitive resin composition will melt | dissolve. In the process of removing and removing the exposed metal layer, the tent film is broken.

Until now, the development of the photosensitive transfer sheet which can form a high resolution pattern and can form the tent film which is hard to be damaged is actively performed, The result is disclosed as follows.

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

Patent Document 2 discloses a photosensitive transfer sheet composed of an alkali-soluble polymer compound, a polymerizable urethane compound having an ethylenically unsaturated bond, a photopolymerizable monomer having three or more ethylenically unsaturated groups in one molecule, and a photopolymerization initiator.

Patent Literature 3 provides a first photosensitive layer which is alkali-soluble on the support, has low fluidity by heating, and is sensitive to active energy rays, and is also alkali-soluble on the support, and has high fluidity by heating. DESCRIPTION OF RELATED ART The photosensitive transfer sheet which has two photosensitive layers which provide the 2nd photosensitive layer sensitive to a line is described. In this patent document, it is explained that the metal layer of the through hole can be protected by filling the second photosensitive layer of the photosensitive transfer sheet into the through hole.

Patent Document 4 describes an example in which a photosensitive resin laminate having a first photosensitive layer and a second photosensitive layer on a support, wherein these two layers have different vinyl copolymers and further contain specific monofunctional monomers in both layers. As an effect, it is described that adhesion and resolution are improved.

Patent Document 5 describes a photoresist having a non-adhesive photosensitive layer and a tacky photosensitive layer on a support, and a method of forming a printed wiring board using the same. As an effect thereof, it is described that the tentability and resolution are improved. have.

Patent Document 6 discloses a photosensitive plate for printing relief manufacture having a photopolymerizable layer (thickness of 25 µm to 2.5 mm) having at least two layers having different photopolymerization rates on a substrate and having a fast polymerization rate on the side close to the substrate. The example which forms the relief image in which the base of a printing surface becomes wider than the uppermost is described.

Patent Document 1: Japanese Patent Application Laid-Open No. 10-142789

(Patent Document 2) Japanese Patent Application Laid-Open No. 2001-117225

Patent Document 3: Japanese Patent Application Laid-Open No. 8-54732

(Patent Document 4) Japanese Patent Application Laid-Open No. 10-111573

(Patent Document 5) Japanese Patent Application Laid-Open No. 3-17650

(Patent Document 6) Japanese Patent Publication No. 37-1306

 An object of the present invention is to provide a photosensitive transfer sheet and a photosensitive laminate which can easily form desired patterns having different thicknesses in an image.

Another object of the present invention is to provide a method that can industrially advantageously form a desired pattern having a different thickness in an image by using a photosensitive transfer sheet or a photosensitive laminate.

An object of the present invention is to provide a photosensitive transfer sheet which is particularly effective for the manufacture of a printed wiring board, capable of forming a tent film that is capable of high resolution by thinning, and which is difficult to be damaged.

Another object of the present invention is to provide a method which can industrially advantageously produce a printed wiring board having hole portions such as through holes and via holes, using a photosensitive transfer sheet.

The present invention firstly comprises a first photosensitive layer comprising a photosensitive resin composition containing a binder, a polymerizable compound and a photopolymerization initiator on a support, and a photosensitive resin composition containing a binder, a polymerizable compound and a photopolymerization initiator, The 2nd photosensitive layer which shows the photosensitivity relatively higher than the photosensitivity of a 1st photosensitive layer is laminated | stacked in this order, and at least one binder of a photosensitive layer is a photosensitive transfer sheet which is a polyurethane resin.

The binder in the photosensitive layer may be used alone or in combination with another binder (for example, a vinyl copolymer). In the case of mixing and using, it is preferable to select a close binder such as polarity so as to mix with each other.

It is preferable that a polyurethane resin has a carboxyl group. Polyurethane resin may be sufficient as the binder of a 1st photosensitive layer. Moreover, polyurethane resin may be sufficient as the binder of a 2nd photosensitive layer. Moreover, polyurethane resin may be sufficient as the binder of a 1st photosensitive layer and a 2nd photosensitive layer.

Preferred embodiments of the first invention are as follows.

(1) A barrier layer is disposed between the first photosensitive layer and the second photosensitive layer.

(2) The barrier layer contains, as a main component, a resin showing affinity for water or lower alcohols having 1 to 4 carbon atoms.

(3) The barrier layer contains, as a main component, a resin soluble in water or a lower alcohol having 1 to 4 carbon atoms.

(4) The barrier layer has a thickness in the range of 0.1 to 5 mu m.

(5) 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.

(6) The ratio represented by A / B of the amount of light energy A required for curing the second photosensitive layer and the amount of light energy B required for curing the first photosensitive layer is in the range of 0.005 to 0.5.

(7) The ratio represented by C / A of the amount of light energy A required for curing the second photosensitive layer and the amount of light energy C required until the curing of the first photosensitive layer starts is in the range of 1 to 10.

(8) Each of the first photosensitive layer and the second photosensitive layer contains a sensitizer.

(9) The amount of the sensitizer contained in the second photosensitive layer is greater than the amount of the sensitizer contained in the first photosensitive layer.

(10) The amount of photoinitiator contained in the second photosensitive layer is greater than the amount of photoinitiator contained in the first photosensitive layer.

(11) The amount of the polymerizable compound contained in the second photosensitive layer is greater than the amount of the polymerizable compound contained in the first photosensitive layer.

(12) The first photosensitive layer has a thickness in the range of 1 to 100 µm, and the thickness thereof is larger than the thickness of the second photosensitive layer.

(13) The second photosensitive layer has a thickness in the range of 0.1 to 15 µm.

(14) The support is made of synthetic resin and is transparent.

(15) The support is a long support.

(16) A protective film is disposed on the second photosensitive layer.

(17) It is a long body, and is wound in roll shape.

(18) It is for manufacturing a printed wiring board.

This invention is 2nd, Comprising: It consists of the 2nd photosensitive layer which consists of a photosensitive resin composition containing a binder, a polymeric compound, and a photoinitiator on a base, and the photosensitive resin composition containing a binder, a polymeric compound, and a photoinitiator, The 1st photosensitive layer which shows the photosensitivity comparatively lower than the photosensitivity of a 2nd photosensitive layer is laminated | stacked in this order, and at least one binder of a photosensitive layer is a photosensitive laminated body which is a polyurethane resin.

Preferred embodiments of the second invention are as follows.

(1) A barrier layer is disposed between the first photosensitive layer and the second photosensitive layer.

(2) The barrier layer contains, as a main component, a resin showing affinity for water or lower alcohols having 1 to 4 carbon atoms.

(3) The barrier layer contains, as a main component, a resin soluble in water or a lower alcohol having 1 to 4 carbon atoms.

(4) The barrier layer has a thickness in the range of 0.1 to 5 mu m.

(5) 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.

(6) The ratio represented by A / B of the amount of light energy A required for curing the second photosensitive layer and the amount of light energy B required for curing the first photosensitive layer is in the range of 0.005 to 0.5.

(7) The ratio represented by C / A of the amount of light energy A required for curing the second photosensitive layer and the amount of light energy C required until the curing of the first photosensitive layer starts is in the range of 1 to 10.

(8) Each of the first photosensitive layer and the second photosensitive layer contains a sensitizer.

(9) The amount of the sensitizer contained in the second photosensitive layer is greater than the amount of the sensitizer contained in the first photosensitive layer.

(10) The amount of photoinitiator contained in the second photosensitive layer is greater than the amount of photoinitiator contained in the first photosensitive layer.

(11) The amount of the polymerizable compound contained in the second photosensitive layer is greater than the amount of the polymerizable compound contained in the first photosensitive layer.

(12) The first photosensitive layer has a thickness in the range of 1 to 100 µm, and the thickness thereof is larger than the thickness of the second photosensitive layer.

(13) The second photosensitive layer has a thickness in the range of 0.1 to 15 µm.

(14) The gas is a substrate for forming a printed wiring board.

(15) A support (particularly preferably a transparent resin film) is laminated on the first photosensitive layer.

(16) It is for manufacturing a printed wiring board.

According to a third aspect of the present invention, there is provided an image including a region in which a cured resin layer is formed by curing the first photosensitive layer and a second photosensitive layer together on a substrate, and a region in which the cured resin layer does not exist. It is a method of forming a pattern.

(1) a step of stacking a photosensitive transfer sheet of the first invention on a substrate in a positional relationship in which the second photosensitive layer is the substrate side to obtain a laminate;

(2) irradiating a predetermined image pattern from the side of the first photosensitive layer of the laminated body, and curing the first photosensitive layer and the second photosensitive layer of the region subjected to the light irradiation together;

(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.

In said 3rd invention, instead of performing a process of removing a support body from the laminated body of (3) between a process (2) and a process (4) as shown below, process (1) and a process ( You may carry out between 2).

Stacking the photosensitive transfer sheet of the first invention on a substrate in a positional relationship in which the second photosensitive layer is the substrate side to obtain a laminate;

Removing the support from the laminate;

Irradiating a predetermined image pattern from the side of the first photosensitive layer of the laminate, and curing the first photosensitive layer and the second photosensitive layer of the region subjected to the light irradiation together; And,

The process of developing a laminated body and removing the unhardened part in a laminated body.

In the third invention, light irradiation is preferably performed by irradiation of laser light.

According to a fourth aspect of the present invention, there is provided a region in which a resin layer formed by curing the first photosensitive layer and the second photosensitive layer together on a substrate including the following steps, and a resin layer formed by curing the second photosensitive layer. It is a method of forming the image pattern comprised from the area | region and the area | region where a cured resin layer does not exist.

(1) a step of obtaining a laminate by laminating the photosensitive transfer sheet of the first invention on a substrate in a positional relationship in which the second photosensitive layer is the substrate side;

(2) From the side of the first photosensitive layer of the laminate, light is irradiated with an image pattern that defines a region for irradiating light of at least two levels of irradiation energy amounts different from each other, and light irradiation with a relatively large amount of light irradiation energy is applied. Curing the first photosensitive layer and the second photosensitive layer of the received region together, and curing the second photosensitive layer of the region subjected to 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.

In said 4th invention, instead of performing a process of removing a support body from the laminated body of (3) between a process (2) and a process (4) as shown below, process (1) and a process ( You may carry out between 2).

Stacking the photosensitive transfer sheet of the first invention on a substrate in a positional relationship in which the second photosensitive layer is the substrate side to obtain a laminate;

Removing the support from the laminate;

From the side of the first photosensitive layer of the laminate, the light is irradiated with an image pattern that defines a region for irradiating light having an amount of irradiation energy of at least two levels which are different from each other, and the region of the region subjected to light irradiation with a relatively large amount of irradiation energy Curing the first photosensitive layer and the second photosensitive layer together, and curing the second photosensitive layer in a region subjected to light irradiation with a relatively small amount of light irradiation energy; And,

The process of developing a laminated body and removing the unhardened part in a laminated body.

In the fourth invention, the light irradiation is preferably performed by the irradiation of laser light.

In the fifth aspect of the present invention, an area covered with a cured resin layer formed by curing the first photosensitive layer and the second photosensitive layer together on a printed circuit board-forming substrate including the following steps and an area where the substrate surface is exposed It is a method of forming a wiring pattern consisting of.

(1) Process of laminating | stacking the photosensitive transfer sheet of said 1st invention on a board | substrate in the positional relationship whose 2nd photosensitive layer becomes a board | substrate side, and obtaining a laminated body;

(2) performing light irradiation of a predetermined wiring pattern from the side of the first photosensitive layer of the laminate, and curing the first photosensitive layer and the second photosensitive layer of the region subjected to the light irradiation together;

(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.

In said 5th invention, instead of performing between the process (2) and the process (4), the process of removing a support body from the laminated body of (3) as shown below is a process (1) and a process. You may carry out between (2).

Stacking the photosensitive transfer sheet of the first invention on a substrate in a positional relationship in which the second photosensitive layer is the substrate side to obtain a laminate;

Removing the support from the laminate;

Irradiating a predetermined wiring pattern from the side of the first photosensitive layer of the laminate, and curing the first photosensitive layer and the second photosensitive layer in the region subjected to the light irradiation together; And,

The process of developing a laminated body and removing the unhardened part in a laminated body.

It is preferable to perform light irradiation in the said 5th invention by irradiation of a laser beam.

According to a sixth aspect of the present invention, a hole portion and a second photosensitive portion are covered with a cured resin layer formed by curing the first photosensitive layer and the second photosensitive layer together on a substrate for forming a printed wiring board including the following steps. It is a method of forming the wiring pattern which consists of the area | region coat | covered with the cured resin layer formed by hardening a layer, and the area | region where the surface of a board | substrate is exposed.

(1) a step of stacking a photosensitive transfer sheet of the first invention on a substrate in a positional relationship in which the second photosensitive layer is the substrate side to obtain a laminate;

(2) From the side of the first photosensitive layer of the laminate, the hole portion is given light irradiation with a relatively large amount of light irradiation energy to cure the first photosensitive layer and the second photosensitive layer together, and to the wiring formation region, the light irradiation Performing light irradiation of an image pattern which gives light irradiation with a relatively small amount of energy to cure the second photosensitive layer;

(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.

In said 6th invention, instead of performing between the process (2) and the process (4), the process of removing a support body from the laminated body of (3) as shown below is a process (1) and a process. You may carry out between (2).

Stacking the photosensitive transfer sheet of the first invention on a substrate in a positional relationship in which the second photosensitive layer is the substrate side to obtain a laminate;

Removing the support from the laminate;

From the side of the first photosensitive layer of the laminate, the hole is irradiated with a relatively large amount of light irradiation energy to cure the first photosensitive layer and the second photosensitive layer together, and the amount of light irradiation energy is relative to the wiring formation region. Performing light irradiation of an image pattern to give a small light irradiation to cure the second photosensitive layer; And,

The process of developing a laminated body and removing the unhardened part in a laminated body.

It is preferable that light irradiation in the said 6th invention is performed by irradiation of a laser beam.

As an example of the photosensitive transfer sheet of this invention, the schematic cross section of the structure which has two layers of photosensitive layers is shown to FIGS.

In FIG. 1, in the photosensitive transfer sheet 10, a support 11, a first photosensitive layer 12, and a second photosensitive layer 14 are stacked in this order. The 1st photosensitive layer 12 and the 2nd photosensitive layer 14 consist of the photosensitive resin composition containing a binder, a polymeric compound, and a photoinitiator, respectively, and harden | cure by light irradiation. The photosensitive transfer sheet of the present invention is mainly characterized in that the second photosensitive layer 14 has a higher light sensitivity than the first photosensitive layer 12. Here, the photosensitivity corresponds to the amount of light energy required to cure each photosensitive layer, and curing of the second photosensitive layer 14 having high photosensitivity is initiated with a light irradiation amount smaller than that of the first photosensitive layer 12, or It means that hardening of the 2nd photosensitive layer 14 is completed by the irradiation amount of light smaller than the 1st photosensitive layer 12. FIG.

In the photosensitive transfer sheet of the present invention, a barrier layer may be disposed between the first photosensitive layer and the second photosensitive layer, and a photosensitive transfer sheet having the barrier layer disposed is preferable. 2 shows a photosensitive transfer sheet further having a barrier layer 13 between the first photosensitive layer 12 and the second photosensitive layer 14.

3 and 4 are photosensitive transfer sheets in which the protective film 15 is further laminated on the photosensitive transfer sheets of FIGS. 1 and 2, respectively.

The thickness of a 1st photosensitive layer, a barrier layer, and a 2nd photosensitive layer can be arbitrarily set according to the objective, respectively. However, it is preferable that the first photosensitive layer has a thickness in the range of 1 to 100 μm, and preferably has a thickness in the range of 5 to 80 μm, and particularly preferably has a thickness in the range of 10 to 50 μm. If the thickness of the first photosensitive layer is thinner than 1 mu m, there may be cases in which it becomes unsuitable for strengthening the film strength. If the thickness exceeds 100 mu m, there may be a problem in development such as development residues tend to remain. . It is preferable that the thickness of the first photosensitive layer is larger than the thickness of the second photosensitive layer.

It is preferable that the barrier layer has a thickness in the range of 0.1 to 5 mu m, further preferably has a thickness in the range of 0.5 to 4 mu m, and particularly preferably has a thickness in the range of 1 to 3 mu m. If the thickness of the barrier layer is thinner than 0.1 mu m, sufficient barrier property may not be obtained. If the thickness exceeds 5 mu m, development takes a long time. It is preferable that the second photosensitive layer has a thickness in the range of 0.1 to 15 mu m, and further preferably has a thickness in the range of 1 to 12 mu m, particularly preferably having a thickness in the range of 3 to 10 mu m. If the thickness of the second photosensitive layer is thinner than 0.1 mu m, thickness unevenness during coating is likely to occur, and if the thickness exceeds 15 mu m, problems such as deterioration in resolution occur.

The layer structure of the photosensitive transfer sheet of this invention is not limited to the layer structure shown in said FIG. 1-4, You may have layers other than the layer shown in FIGS. For example, the layer which adjusts peelability and adhesive force with a support body and a board | substrate between the support body 11 and the 1st photosensitive layer 12, or between the protective film 15 and the 2nd photosensitive layer 14, for example. , An anti-halation layer, or a barrier layer may be formed. In this case, the barrier layer has a role of preventing or suppressing external influences such as migration or prevention of migration of substances contained in the photosensitive layer, the support, or the protective film, oxygen or humidity, and the like.

Next, the relationship between the irradiation amount of light and the hardening amount of the photosensitive layer in the photosensitive transfer sheet and the photosensitive laminated body of this invention is demonstrated, referring FIG. FIG. 5 shows, for example, when the photosensitive transfer sheet obtained by peeling a protective film from the photosensitive transfer sheet shown in FIG. 1 or the photosensitive transfer sheet shown in FIG. 3 is transferred onto a substrate to form a laminate. On the other hand, when the support body is provided from the side opposite to the substrate, the amount of light irradiation, the irradiation (exposure), and It is a graph (sensitivity curve) which shows the relationship with the thickness of the hardened layer produced | generated by the following image development process. In FIG. 5, the horizontal axis shows the irradiation amount of light, and the vertical axis shows the thickness of the hardened layer obtained after hardening by irradiation of light and performing image development processing. D on the vertical axis represents the thickness of the cured layer formed from the second photosensitive layer, and E represents the thickness of the sum of the thickness of the cured layer formed from the first photosensitive layer and the thickness of the cured layer formed from the second photosensitive layer.

As shown in FIG. 5, in the photosensitive transfer sheet of the present invention, the light irradiated from the support side has a second photosensitive light in the case of having a support, in spite of the support, the first photosensitive layer, and the second photosensitive layer. Curing of the layer is started with a small amount of light energy before the first photosensitive layer. After the whole of the second photosensitive layer is cured, when the amount of light energy increases, curing of the first photosensitive layer starts, and when the amount of light energy increases, the whole of the 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 light sensitivity of the first photosensitive layer is 1, it is preferable that the photosensitivity of the second photosensitive layer is in the range of 2 to 200, It is more preferable to exist in the range of 2.5-100, and it is especially preferable to exist in the range of 3-50.

The amount of light energy C required until the curing of the first photosensitive layer starts may be the same amount as the amount of light energy A required to cure the second photosensitive layer, but is preferably larger than the amount of light energy A.

Like the photosensitive transfer sheet shown in Figs. 2 and 4, even when a barrier layer is provided between the first photosensitive layer and the second photosensitive layer, the relationship between the irradiation amount of light and the thickness of the cured layer as shown in Fig. 5 is obtained. In this case, however, the film thickness E represents a thickness obtained by adding the thickness of the barrier layer to the thickness of the cured layer formed from the first photosensitive layer and the thickness of the cured layer formed from the second photosensitive layer.

Moreover, the photosensitive transfer sheet of this invention may have two or more photosensitive layers. As an example, sectional drawing in the case of three photosensitive layers is shown in FIG. In addition, the case where a barrier layer is provided between each photosensitive layer is shown in FIG. 7, the case where it has a protective film on the photosensitive layer of FIG. 6, and the case where it has a protective film 56 on the photosensitive layer of FIG. 9 is shown.

In the photosensitive transfer sheet 50 of FIGS. 6-9, the support body is represented by 51, and on the support body 51, the 1st photosensitive layer 52, the 2nd photosensitive layer 54, and the 1st The three photosensitive layers 55 are laminated sequentially. In the photosensitive transfer sheet 50 of FIG. 7, the barrier layer is respectively between the first photosensitive layer 52 and the second photosensitive layer 54, and between the second photosensitive layer 54 and the third photosensitive layer 55. 53 is formed. FIG. 8 shows a configuration in which the protective layer 56 is formed in the photosensitive transfer sheet in FIG. 6, and FIG. 9 shows a configuration in which the protective layer 56 is formed in the photosensitive transfer sheet in FIG. 7.

Also in the case of these three-layer photosensitive layer constitution, each photosensitive layer becomes relatively high in the sensitivity of the photosensitive layer of the side far from a support body compared with the sensitivity of the photosensitive layer of the side near a support body. That is, the sensitivity of the photosensitive layer is the highest in the third photosensitive layer, followed by the second photosensitive layer, and the lowest in the first photosensitive layer.

Using the photosensitive transfer sheet of the structure shown in FIGS. 6-9, the light energy amount X which hardens only a 3rd photosensitive layer according to the area | region which needs the amount of light energy used for pattern formation, 3rd photosensitive layer, and 2nd As shown in FIG. 10, by varying the amount of light energy Y for curing the photosensitive layer Y, the third photosensitive layer, the second photosensitive layer, and the first photosensitive layer Z, and the amount of light irradiation, the substrate 57 ), An area having a thickness cured only by the third photosensitive layer 55, an area having a thickness cured by the third photosensitive layer 55 and the second photosensitive layer 54, a third photosensitive layer 55, A pattern having three different thicknesses, that is, a region having a cured thickness of both the second photosensitive layer 54 and the first photosensitive layer 52 can be formed of one kind of photosensitive transfer sheet.

Similarly, when the photosensitive layer is N layer (the number of photosensitive layers is N), and the photosensitive transfer sheet | seat with a higher sensitivity of the photosensitive layer farther from a support body is used compared with the sensitivity of the photosensitive layer of the side near a support body, A cured layer pattern having different thicknesses of N steps can be formed by one kind of photosensitive transfer sheet.

As described so far, the photosensitive transfer sheet of the present invention can make the thickness of the cured layer obtained by exposure and development treatment to a desired thickness according to the exposure amount (so-called light energy amount), and the pattern of the exposure amount. By changing as needed, it is possible to divide and make from the area | region which hardens only the photosensitive layer closest to a board | substrate to the area | region which hardens all the photosensitive layers by changing thickness sequentially. Therefore, one type of photosensitive transfer is performed on a three-dimensional molding having a different thickness inside the image, a cured resin image or the like which gives characteristics such as increasing the intensity of the film of only the desired area or increasing the image density only of the desired area. It becomes possible to form into a sheet.

Therefore, when the photosensitive transfer sheet of the present invention is used in the manufacture of a printed wiring board, in particular in the manufacture of a printed wiring board having through holes or via holes, a relatively thin and high resolution hardened layer is formed in the wiring pattern formation region, and the through holes are formed. Alternatively, the via hole may have a relatively thick and high strength hardened layer. Therefore, by using the photosensitive transfer sheet of the present invention, a cured resin pattern with sufficient resolution can be easily formed at a portion having sufficient tent film strength that can be used as a tenting method and high resolution is required.

According to the present invention, it has been found that the photosensitive transfer sheet having a sensitivity curve as described above can be realized by relatively high in order as the sensitivity of each photosensitive layer is directed from the side close to the support toward the side away from the support. . As the method of making this photosensitive layer two or more layers, and increasing the sensitivity of those photosensitive layers sequentially, all the well-known high sensitivity techniques can be used. That is, for example, the use of a high-sensitivity initiator, the use of a sensitizer, the increase in the content of the photopolymerization initiator and / or the sensitizer, or the content of the polymerizable compound in the photosensitive layer is increased, or the ratio of the polymerization inhibitor or the polymerization inhibitor is increased. It can be obtained by a method such as decreasing. In particular, when the photosensitive layer is two layers, in addition to using a high-sensitivity initiator, for example, a sensitizer may be added to the second photosensitive layer, or the content of the photopolymerization initiator and / or the sensitizer in the second photosensitive layer may be changed to the first. It can also be obtained by a method such as increasing the photosensitive layer or increasing the content of the polymerizable compound in the second photosensitive layer than the first photosensitive layer.

The photosensitive resin composition containing the 1st photosensitive layer which consists of a photosensitive resin composition containing a binder, a polymeric compound, and a photoinitiator on the support body of this invention, a binder, a polymeric compound, and a photoinitiator, An image pattern using a photosensitive transfer sheet formed by stacking a second photosensitive layer having a light sensitivity relatively higher than that of a photosensitive layer, or a photosensitive transfer sheet having a barrier layer disposed between the first photosensitive layer and the second photosensitive layer. be in the range of (the cured resin pattern) the case of forming the second photosensitive layer, the light energy amount S is, 0.05~10mJ / cm ² is preferable and, 0.1~5mJ / cm ² in the range of the curing starts in More preferably, it is especially preferable to exist in the range of 0.15-2.5mJ / cm <^2> . In the second light amount of energy necessary to cure the photosensitive layer A is, more preferably in the range of desirable and, 0.2~15mJ / cm ² in the range of 0.1~20mJ / cm ² and, 0.4~10mJ / cm It is especially preferable that it is the range of ² .

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 required to cure the first photosensitive layer is preferably in the range of 0.005 to 0.5, preferably 0.01 to 0.4. It is more preferable to exist in the range of, and it is especially preferable to exist in the range of 0.02-0.35. And it is preferable that ratio (C / A) of the amount of light energy A required in order to harden a 2nd photosensitive layer and the amount of light energy C required until hardening of a 1st photosensitive layer starts is in the range of 1-10, It is more preferable to exist in the range of 1.1-9, and it is especially preferable that it is the range of 1.3-8. Further, the light energy amount of C is, 0.1~200mJ / cm ² preferably in the range of, more preferably in the range of 1~100mJ / cm ^2, and in the range of 2~50mJ / cm ^2, particularly preferably Do.

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

[bookbinder]

Polyurethane resin is used for the binder of a 1st photosensitive layer and / or a 2nd photosensitive layer. The binder of either photosensitive layer of a 1st photosensitive layer and a 2nd photosensitive layer may be a polyurethane resin, and the binder of both photosensitive layers may be a polyurethane resin. It is preferable that all the binders of both photosensitive layers are polyurethane resins.

It is preferable that a polyurethane resin is soluble in alkaline aqueous solution, or it is preferable to have at least swelling property. The polyurethane resin is based on a structural unit represented by a reaction product of at least one of the diisocyanate compounds represented by the following general formula (2) and at least one of the diol compounds represented by the general formula (3). It is preferable that it is a polyurethane resin.

OCN-X ⁰ -NCO (2)

HO-Y ⁰ -OH (3)

(Wherein, X ⁰ , Y ⁰ represent a divalent organic residue.)

Preferable as the isocyanate compound is a diisocyanate compound represented by the following General Formula (4).

OCN-L ¹ -NCO (4)

In the formula, L ¹ represents a divalent aliphatic or aromatic hydrocarbon group which may have a substituent. As needed, L <^1> may have another functional group which does not react with an isocyanate group, for example, ester, urethane, amide, and ureido group.

i) diisocyanate compounds

Specifically as a diisocyanate compound represented by the said General formula (4), what is shown below is contained. In other words, 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane Aromatic diisocyanate compounds such as diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate and the like; Aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate and the like; Alicyclic diisocyanates such as isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatemethyl) cyclohexane compound; Diisocyanate compounds which are reactants of diols and diisocyanates such as adducts of 1 mole of 1,3-butylene glycol and 2 moles of tolylene diisocyanate; And the like.

ii) diol compounds

As a diol compound, a polyether diol compound, a polyester diol compound, a polycarbonate diol compound, etc. are mentioned widely. As a polyether diol compound, the random copolymer of the compound represented by following formula (5), (6), (7), (8), (9), and the ethylene oxide and propylene oxide which has a hydroxyl group at the terminal is Listed.

In formula, R <^1> is a hydrogen atom or a methyl group, X represents the following groups.

A, b, c, d, e, f and g each represent an integer of 2 or more, preferably an integer of 2 to 100;

Specific examples of the polyetherdiol compound represented by the formulas (5) and (6) include the following. That is, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, di-1,2-propylene glycol, tri-1,2-propylene glycol, tetra -1,2-propylene glycol, hexa-1,2-propylene glycol, di-1,3-propylene glycol, tri-1,3-propylene glycol, tetra-1,3-propylene glycol, di-1,3- Butylene glycol, tri-1, 3- butylene glycol, hexa-1, 3- butylene glycol, polyethylene glycol of the weight average molecular weight 1000, polyethylene glycol of the weight average molecular weight 1500, polyethylene glycol of the weight average molecular weight 2000, weight average Polyethylene glycol of molecular weight 3000, polyethylene glycol of weight average molecular weight 7500, polypropylene glycol of weight average molecular weight 400, polypropylene glycol of weight average molecular weight 700, polypropylene glycol of weight average molecular weight 1000, weight average molecule 2000 is a polypropylene glycol, weight average molecular weight of 3000 of the polypropylene glycol, the weight average molecular weight of 4,000 of the polypropylene glycol and the like.

Specifically as a polyetherdiol compound represented by Formula (7), what is shown below is mentioned. Sanyo Kasei Kogyo Co., Ltd., (brand name) PTMG 650, PTMG 1000, PTMG 2000, PTMG 3000.

Specifically as a polyetherdiol compound represented by Formula (8), what is shown below is mentioned. Sanyo Kasei Bridge Co., Ltd., (brand name) New Fall PE-61, New Fall PE-62, New Fall PE-64, New Fall PE-68, New Fall PE-71, New Fall PE-74, New Fall PE-75, New Fall PE-78 , Newpole PE-108, Newpole PE-128, Newpole PE-61, etc.

Specifically as a polyetherdiol compound represented by Formula (9), what is shown below is mentioned. Sanyo Kasei Bridge Co., Ltd., (brand name) New Pole BPE-20, New Pole BPE-20F, New Pole BPE-20NＫ, New Pole BPE-20T, New Pole BPE-20G, New Pole BPE-40, New Pole BPE-60, New Pole BPE-100 , Newpole BPE-180, Newpole BPE-2P, Newpole BPE-23P, Newpole BPE-3P, Newpole BPE-5P etc.

As a random copolymer of ethylene oxide and propylene oxide which have a hydroxyl group at the terminal, what is shown below is specifically mentioned. Sanyo Kasei Kogyo Co., Ltd. (brand name) New Pole 50HB-100, New Pole 50HB-260, New Pole 50HB-400, New Pole 50HB-660, New Pole 50HB-2000, New Pole 50HB-5100.

As a polyesterdiol compound, the compound represented by Formula (10) and (11) is mentioned.

In formula, L <^2> , L <^3> and L <^4> represent the divalent aliphatic or aromatic hydrocarbon group which may be the same respectively, and L <^5> represents the divalent aliphatic hydrocarbon group. Preferably, L ² , L ³ , and L ⁴ each represent an alkylene group, an alkenylene group, an alkynylene group, an arylene group, and L ⁵ represents an alkylene group. In addition, other functional groups which do not react with isocyanate groups, such as ethers, carbonyls, esters, cyanos, olefins, urethanes, amides, ureido groups or halogen atoms, are present in L ² , L ³ , L ⁴ , and L ^5. You may do it. n1 and n2 are integers 2 or more, respectively, Preferably the integer of 2-100 is represented.

As a polycarbonate diol compound, there exists a compound represented by Formula (12).

In the formula, L ⁶ may be the same as or different from each other, and represents a divalent aliphatic or aromatic hydrocarbon group. Preferably, L ⁶ represents an alkylene group, an alkenylene group, an alkynylene group, an arylene group. In addition, other functional groups that do not react with isocyanate groups, such as ether, carbonyl, ester, cyano, olefin, urethane, amide, ureido group, or halogen atom, may be present in L ⁶ . n3 is an integer of 2 or more, Preferably it represents the integer of 2-100.

Specific examples of the diol compound represented by the formulas (10), (11) and (12) include the following (Example Compound No. 1) to (Example Compound No. 18). N in a specific example is an integer of 2 or more.

The polyurethane resin (urethane binder) used when the photosensitive transfer sheet of this invention is used for manufacture of a printed wiring board, More preferably, it is a polyurethane resin which has a carboxyl group further. As a polyurethane resin used preferably, the structural unit represented by at least 1 sort (s) of the diol compound of Formula (13), (14), (15) and / or the compound which ring-opened tetracarboxylic dianhydride with a diol compound The polyurethane resin which has a structural unit derived from is mentioned.

In the formula, R ² represents a hydrogen atom, a substituent (for example, a cyano group, a nitro group, a halogen atom such as -F, -Cl, -Br, -I, -CONH ₂ , -COOR ³ , -OR ³ , -NHCONHR ³ , -NHCOOR ³ , -NHCOR ³ , -OCONHR ³ (wherein R ₃ includes an alkyl group having 1 to 10 carbon atoms and an aralkyl group having 7 to 15 carbon atoms). Good alkyl group, aralkyl group, aryl group, alkoxy group, aryloxy group is shown, Preferably a hydrogen atom, a C1-C8 alkyl group, and a C6-C15 aryl group are shown. L ⁷ , L ⁸ , L ⁹ may be the same as or different from each other, and a divalent aliphatic or aromatic group which may have a single bond, a substituent (for example, alkyl, aralkyl, aryl, alkoxy, or halogeno group is preferable). A hydrocarbon group is shown, Preferably it is a C1-C20 alkylene group, a C6-C15 arylene group, More preferably, a C1-C8 alkylene group is shown. Moreover, as needed, you may have other functional groups which do not react with an isocyanate group in L <^7> , L <^8> , L <^9> , for example, carbonyl, ester, urethane, amide, ureido, and ether group. In addition, you may form a ring by two or three of R <^2> , L <^7> , L <^8> , L <^9> . Ar represents the trivalent aromatic hydrocarbon group which may have a substituent, Preferably it represents a C6-C15 aromatic group.

iii) Diol compound containing a carboxyl group As the diol compound which has a carboxyl group represented by Formula (13), (14) or (15), what is shown below is specifically included. Namely, 3,5-dihydroxy benzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid , Bis (hydroxymethyl) acetic acid, bis (4-hydroxyphenyl) acetic acid, 2,2-bis (hydroxymethyl) butyric acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, N, N-dihydroxyethylglycine, N, N-bis (2-hydroxyethyl) -3-carboxy-propionamide, and the like.

In this invention, what is represented by Formula (16), (17), (18) is mentioned as preferable tetracarboxylic dianhydride used for the synthesis | combination of a polyurethane resin.

In the formula, L ¹⁰ is a divalent aliphatic or aromatic hydrocarbon group which may have a single bond, a substituent (for example, each group of alkyl, aralkyl, aryl, alkoxy, halogeno, ester, and amide is preferred)- CO-, -SO-, -SO _2- , -O-, or -S- represents, preferably, a single bond, a divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, -CO-, -SO ₂ -,- O- or -S- is represented. R <^4> , R <^5> may be same or different, and represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, or a halogeno group, Preferably, a hydrogen atom, a C1-C8 alkyl group, C6-C15 An aryl group, a C1-C8 alkoxy group, or halogeno group is shown. In addition, two of L ¹⁰ , R ⁴ and R ^{5 may be} bonded to each other to form a ring.

R <^6> , R <^7> may be same or different, and represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a halogeno group, Preferably it represents a hydrogen atom, a C1-C8 alkyl, or a C6-C15 aryl group. In addition, two of L ¹⁰ , R ⁶ , and R ⁷ may combine to form a ring. L ¹¹ and L ¹² may be the same or different and represent a single bond, a double bond or a divalent aliphatic hydrocarbon group, and preferably a single bond, a double bond, or a methylene group. A represents a mononuclear or multinuclear aromatic ring. Preferably, a C6-C18 aromatic ring is represented.

As a compound represented by Formula (16), (17) or (18), what is shown below is specifically included. That is, pyromellitic dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 3,3', 4,4'- diphenyl tetracarboxylic dianhydride, 2,3, 6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, 2,2-bis (3,4-di Carboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 4,4 '-[3,3'-(alkylphosphoryldiphenylene) -bis (iminocarbonyl)] di Phthalic acid dianhydride,

Aromatic tetracarboxylic dianhydrides such as adducts of hydroquinone diacetate and trimellitic anhydride and adducts of diacetyldiamine and trimellitic anhydride; 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride (Dinipon Ink Chemical Co., Ltd., Epikron B-4400) Alicyclic tetra, such as 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and tetrahydrofurantetracarboxylic dianhydride Carboxylic dianhydride; And aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride and 1,2,4,5-pentanetetracarboxylic dianhydride.

As a method of introduce | transducing the structural unit derived from the compound which opened these tetracarboxylic dianhydride with the diol compound in a polyurethane resin, the following method is mentioned, for example.

a) The method of making the alcohol terminal compound obtained by ring-opening tetracarboxylic dianhydride with a diol compound, and a diisocyanate compound.

b) The method in which the urethane compound of the alcohol terminal obtained by making a diisocyanate compound react on excess conditions of a diol compound, and tetracarboxylic dianhydride are made to react.

In addition, as a diol compound used at this time, what is specifically shown below is included. That is, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butylene glycol, 1,6-hexanediol, 2-butene-1,4-diol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecanedimethanol , Hydrogenated bisphenol A, hydrogenated bisphenol F, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol F, propylene oxide adduct of bisphenol F, hydrogenated bisphenol Ethylene oxide adduct of A, propylene oxide adduct of hydrogenated bisphenol A, hydroquinonedihydroxyethyl ether, p-xylylene glycol, dihydroxyethyl sulfone, bis (2-hydroxyethyl) -2, 4-tolylenecarbamate, 2,4-tolylene -Bis (2-hydroxyethylcarbamide), bis (2-hydroxyethyl) -m-xylylenedicarbamate, bis (2-hydroxyethyl) isophthalate, and the like.

iv) For the synthesis of other diol compounds or polyurethane resins, other diol compounds which may not have a carboxyl group and may have other substituents which do not react with isocyanates may be used in combination. As such a diol compound, what is shown below is contained.

HO-L ¹³ -O-CO-L ¹⁴ -CO-OL ¹³ -OH (19)

HO-L ¹⁴ -CO-OL ¹³ -OH (20)

In formula, L <^13> , L <^14> may be same or different, respectively and is a halogen atom, such as a substituent (for example, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, -F, -Cl, -Br, -I) Each group, such as etc. is included.), The bivalent aliphatic hydrocarbon group, aromatic hydrocarbon group, or heterocyclic group which may have is shown. If necessary, L ^13, L, for different functional groups, for example, that do not react with isocyanate groups in the ^14, may have a carbonyl group, an ester group, a urethane group, an amide group, a ureido group or the like. It is also possible to form a ring with L ^13, L ^14.

In addition, as a specific example of a compound represented by said Formula (19) or (20), (Example compound No. 19)-(Example compound No. 35) shown below are included.

Moreover, the diol compound represented by Formula (21) and Formula (22) below can also be used preferably.

In formula, R <^8> , R <^9> may be same or different, respectively, Alkyl group, an aralkyl group, an aryl group, -COOR, -OR, -NHCONHR, -NHCOOR, -NHCOR, -OCONHR (where R is C1-C20) Alkyl group (linear alkyl group, branched alkyl group, cyclic alkyl group), aralkyl group having 7 to 20 carbon atoms, and aryl group having 6 to 20 carbon atoms. Preferably, they are a C1-C8 alkyl group, a C6-C15 aryl group, or -NHCOR.

c represents an integer of 2 or more, Preferably it is an integer of 2-100.

Specific examples of the diol compounds represented by the formulas (21) and (22) include those shown below. In other words, as formula (21), ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octane As formula (22), such as diol, it is a compound etc. which are shown below.

Moreover, the diol compound represented by following formula (23) and formula (24) can also be used preferably.

HO-L ¹⁵ -NH-CO-L ¹⁶ -CO-NH-L ¹⁵ -OH (23)

HO-L ¹⁶ -CO-NH-L ¹⁵ -OH (24)

In formula, L <^15> , L <^16> may respectively be same or different, and each of substituents (for example, alkyl, aralkyl, aryl, alkoxy, aryloxy, halogen atom (-F, -Cl, -Br, -I), etc.). And divalent aliphatic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group which may have As needed, you may have other functional groups which do not react with an isocyanate group in L <^15> , L <^16> , for example, carbonyl, ester, urethane, amide, ureido group, etc. In addition, you may form a ring by L <^15> , L <^16> .

In addition, what is shown below is included as a specific example of a compound represented by Formula (23) or (24).

Moreover, the diol compound represented by following formula (25) and formula (26) can also be used preferably.

HO-Ar ^2- (L ¹⁷ -Ar ³ ) n-OH (25)

HO-Ar ² -L ¹⁷ -OH (26)

In formula, L <^17> represents the bivalent aliphatic hydrocarbon group which may have a substituent (For example, each group of alkyl, aralkyl, aryl, alkoxy, aryloxy, and halogeno is preferable.). If necessary, L ^17, for isocyanate group and other functional groups do not react, for example, during, or may have an ester, urethane, amide, ureido group. Ar <^2> , Ar <^3> may be same or different, and represents the bivalent aromatic hydrocarbon group which may have a substituent, Preferably it represents a C6-C15 aromatic group. n represents the integer of 0-10.

In addition, as a diol compound represented by said Formula (25) or (26), what is specifically shown below is included. That is, catechol, resorcin, hydroquinone, 4-methylcatechol, 4-t-butylcatechol, 4-acetylcatechol, 3-methoxycatechol, 4-phenylcatechol, 4-methylresorcin, 4-ethylresorcin, 4-t-butylresorcin, 4-hexyl resorcin, 4-chlororesorcin, 4-benzylesorcin, 4-acetylresorcin, 4-carbomethoxyresorcin, 2-methylresor Lecin, 5-methylresorcin, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, tetramethylhydroquinone, tetrachlorohydroquinone, methylcar Boaminohydroquinone, methylureidohydroquinone, methylthiohydroquinone, benzonorbornene-3,6-diol, bisphenol A,

Bisphenol S, 3,3'-dichlorobisphenol S, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxybiphenyl, 4,4'-thiodiphenol, 2,2'-dihydrate Oxydiphenylmethane, 3,4-bis (p-hydroxyphenyl) hexane, 1,4-bis (2- (p-hydroxyphenyl) propyl) benzene, bis (4-hydroxyphenyl) methylamine, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,5-dihydroxyanthraquinone, 2-hydroxy Benzyl alcohol, 4-hydroxybenzyl alcohol, 2-hydroxy-3,5-di-t-butylbenzyl alcohol, 4-hydroxy-3,5-di-t-butylbenzyl alcohol, 4-hydroxyphenethyl Alcohols, 2-hydroxyethyl-4-hydroxybenzoate, 2-hydroxyethyl-4-hydroxyphenyl acetate, resorcin mono-2-hydroxyethyl ether and the like. The diol compound shown by following formula (27), formula (28), or formula (29) can also be used preferably.

Wherein R ¹⁰ represents a hydrogen atom, a substituent (for example, cyano, nitro, halogen atom (-F, -Cl, -Br, -I), -CONH ₂ , -COOR ¹¹ , -OR ¹¹ , -NHCONHR ¹¹ , -NHCOOR ¹¹ , -NHCOR ¹¹ , -OCONHR ¹¹ , -CONHR ¹¹ (wherein R ¹¹ includes an alkyl group having 1 to 10 carbon atoms and an aralkyl group having 7 to 15 carbon atoms). The alkyl, aralkyl, aryl, alkoxy, and aryloxy groups which may have a substituent are represented, and preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms and an aryl group having 6 to 15 carbon atoms. L ¹⁸ , L ¹⁹ , L ²⁰ may be the same as or different from each other, and a divalent aliphatic or aromatic hydrocarbon which may have a single bond, a substituent (for example, each group of alkyl, aralkyl, aryl, alkoxy and halogen is preferable). Group, Preferably they are a C1-C20 alkylene group, a C6-C15 arylene group, More preferably, a C1-C8 alkylene group is shown. , L ^18, L ^19, L ^20, for the isocyanate group and other functional groups do not react, for example, carbonyl, may have an ester, urethane, amide, ureido, ether groups, if necessary. In addition, you may form a ring by two or three of R <^10> , L <^18> , L <^19> , L <^20> . Ar represents the trivalent aromatic hydrocarbon group which may have a substituent, Preferably it represents a C6-C15 aromatic group. Z ⁰ represents the following group.

Here, R <^12> , R <^13> may be same or different, respectively, and represents a hydrogen atom, sodium, potassium, an alkyl group, and an aryl group, Preferably they represent a hydrogen atom, an alkyl group of 1-8 carbon atoms, and an aryl group of 6-15 carbon atoms.

The diol compound which has the phosphonic acid, phosphoric acid, and / or these ester groups represented by said Formula (27), (28) or (29) is synthesize | combined by the method shown below, for example. After protecting the hydroxy groups of the halogen compounds represented by the following general formulas (30), (31) and (32) as necessary, phosphonate esterification is carried out by the Michaelis-Arbuzov reaction represented by the formula (33). In addition, synthesis is carried out by hydrolysis with hydrogen fluoride or the like as necessary.

In formula, R <^14> , L <^21> , L <^22> , L <^23> and Ar have the same meaning as the case of Formula (27), (28), (29). R <^15> represents an alkyl group and an aryl group, Preferably, they are a C1-C8 alkyl group and a C6-C15 aryl group. R ¹⁶ is a residue except X ¹ in formulas (30), (31) and (32), and X ¹ represents a halogen atom, preferably Cl, Br, or I.

Moreover, synthesis | combination is performed by reaction to hydrolyze after reaction with phosphorus oxychloride represented by Formula (34).

In the formula, R ¹⁷ has the same meaning as in the formula (33), and M represents a hydrogen atom, sodium or potassium.

When the polyurethane resin of this invention has a phosphonic acid group, the diol which has the diisocyanate compound represented by the said General formula (4), and the phosphonic acid ester group represented by said Formula (27), (28) or (29) The compound may be reacted to form a polyurethane resin, and then synthesized by hydrolysis with hydrogen fluoride or the like.

Moreover, the amino group containing compound shown below may also be made to react with the diisocyanate compound represented by General formula (4) similarly to a diol compound, to form a urea structure, and to combine it with the structure of a polyurethane resin.

In formula, R <^18> , R <^19> may be same or different, respectively, and each group, such as a hydrogen atom and a substituent (for example, alkoxy, a halogen atom (-F, -Cl, -Br, -I), ester, a carboxyl group, is included) The alkyl, aralkyl, and aryl groups which may have.) Are preferably represented, and preferably, the C1-8 alkyl and C6-C15 aryl groups which may have a carboxyl group as a hydrogen atom and a substituent. L ²⁴ may have a substituent (for example, each group such as alkyl, aralkyl, aryl, alkoxy, aryloxy, halogen atom (-F, -Cl, -Br, -I), carboxyl group, etc. may be included). A divalent aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group is shown. Necessary, L ^24, for the other functional groups, for example, which does not react with isocyanate groups, carbonyl, may have an ester, urethane, amide group, and the like in accordance with the. In addition, you may form a ring by two of R <^18> , L <^24> , and R <^19> .

In addition, what is shown below is contained as a specific example of a compound represented by General formula (35) and (36). That is, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, dodecamethylenediamine, propane-1,2-diamine, bis (3-aminopropyl) methylamine , 1,3-bis (3-aminopropyl) tetramethylsiloxane, piperazine, 2,5-dimethylpiperazine, N- (2-amino ethyl) piperazine, 4-amino-2,2-6,6- Aliphatic diamine compounds such as tetramethylpiperidine, N, N-dimethylethylenediamine, lysine, L-cystine, isophorone diamine and the like;

o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, benzidine, o-ditoluidine, o-diazinidine, 4-nitro-m-phenylenediamine, 2 , 5-dimethoxy-p-phenylenediamine, bis- (4-aminophenyl) sulfone, 4-carboxy-o-phenylenediamine, 3-carboxy-m-phenylenediamine, 4,4'-diaminophenyl Aromatic diamine compounds such as ether, 1,8-naphthalenediamine and the like; 2-aminoimidazole, 3-aminotriazole, 5-amino-1H-tetrazole, 4-aminopyrazole, 2-aminobenzimidazole, 2-amino-5-carboxy-triazole, 2,4-dia Heterocyclic amine compounds such as mino-6-methyl-S-triazine, 2,6-diaminopyridine, L-histidine, DL-tryptophan, adenine and the like;

Ethanolamine, N-methylethanolamine, N-ethylethanolamine, 1-amino-2-propanol, 1-amino-3-propanol, 2-aminoethoxyethanol, 2-aminothioethoxyethanol, 2-amino- 2-methyl-1-propanol, p-aminophenol, m-aminophenol, o-aminophenol, 4-methyl-2-aminophenol, 2-chloro-4-aminophenol, 4-methoxy-3-aminophenol , 4-hydroxybenzylamine, 4-amino-1-naphthol, 4-aminosalicylic acid, 4-hydroxy-N-phenylglycine, 2-aminobenzyl alcohol, 4-aminophenethyl alcohol, 2-carboxy-5- Aminoalcohol or aminophenol compounds such as amino-1-naphthol, L-tyrosine and the like.

The polyurethane resin which can be used for this invention is synthesize | combined by adding the well-known catalyst of the activity according to each reactivity in an aprotic solvent, and heating the said isocyanate compound and diol compound. The molar ratio of the diisocyanate to be used and the diol compound is preferably 0.8: 1 to 1.2: 1. When an isocyanate group remains at the polymer terminal, it is synthesized into a form in which no isocyanate group is finally left by treating with an alcohol or an amine. .

Polyurethane resin is also preferably used having an unsaturated bond in the polymer terminal, main chain, side chain. By having an unsaturated bond, a crosslinking reaction arises between a polymeric compound and a polyurethane resin, As a result, photocuring intensity increases and a tent film with high strength can be provided. As the unsaturated bond, a carbon-carbon double bond is particularly preferable from the ease of crosslinking reaction.

As a method of introducing an unsaturated group into a polymer terminal, there exists a method shown below. That is, when an isocyanate group remains in the polymer terminal in the synthesis | combination process of the polyurethane resin mentioned above, in the process of processing by alcohol or amines, alcohol, amine, etc. which have an unsaturated group may be used. As such a compound, the following can be specifically mentioned.

As a method of introducing an unsaturated group into a main chain and a side chain, there exists a method of using the diol compound which has an unsaturated group for polyurethane resin synthesis | combination. Specific examples of the diol compound having an unsaturated group include the following compounds. Diol compound represented by Formula (37) or (38). Specifically, what is shown below is enumerated.

As a diol compound represented by Formula (37), specifically, as a diol compound represented by Formula (38), 2-butene-1,4-diol etc. are cis-2-butene-1,4-diol, trans-2-butene-1,4-diol and the like.

As a diol compound which has an unsaturated group in a side chain, the compound specifically, shown below can be mentioned.

Polyurethane resin, Preferably, it contains an aromatic group in a main chain and / or a side chain. More preferably, content of an aromatic group is 10 to 80 weight% of a polyurethane resin. It is preferable that such polyurethane resin is a polyurethane resin which has a carboxyl group, It is preferable that the content contains 0.4 meq / g or more of carboxyl groups, More preferably, it is the range of 0.4-3.5 meq / g. Moreover, as molecular weight of a polyurethane resin, Preferably it is 1000 or more in weight average molecular weight, More preferably, it is the range of 1000,000-300,000.

Polyurethane resin may be used independently, or may mix and use 2 or more types.

You may use together a polyurethane resin and another binder.

It is preferable that the binder of the photosensitive layer which is not a polyurethane resin is soluble in alkali aqueous solution, or it is preferable to have at least swelling property. As an example of such a binder, what has an acidic group (carboxyl group, sulfonic acid group, phosphoric acid group, etc.) can be used, Especially the binder which has a carboxyl group is typical, For example, a carboxyl group-containing vinyl copolymer and a carboxyl group-containing polyurethane resin Although a polyamic acid resin, a modified epoxy resin, etc. can be mentioned, A carboxyl group-containing vinyl copolymer is preferable from the solubility to a coating solvent, the solubility to alkaline developing solution, the synthetic suitability, the ease of adjustment of a film | membrane property, etc.

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

Examples of the carboxyl group-containing vinyl monomers include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimers, and the like. Moreover, addition reaction of the monomer which has hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, and cyclic anhydrides, such as maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride, (omega)-carboxy- polycaprolactone mono (Meth) acrylate etc. can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, a citraconic anhydride, as a precursor of a carboxyl group. Among these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility and the like.

There is no restriction | limiting in particular as another copolymerizable monomer which can be used for the synthesis | combination of the said copolymer, As an example of such a monomer, For example, (meth) acrylic acid ester, crotonic acid ester, vinyl ester, maleic acid diester, Fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable. As such an example, the following compounds are enumerated, for example.

As an example of (meth) acrylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, iso Butyl (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, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy- 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol hair Methyl 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, polyethyleneglycol monomethyl ether (meth) acrylate, polyethyleneglycol monoethylether (meth) acrylate, β-phenoxyethoxyethyl acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, dish Clopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, Perfluorooctylethyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) Such as methacrylate are exemplified.

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

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

As (meth) acrylamide, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide , Nn-butylacryl (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) acryloyl morpholine, diacetone acrylamide, etc. Listed.

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, chloro styrene, dichloro styrene and bromo Styrene, chloromethylstyrene, hydroxystyrene protected by a group which can be deprotected by an acidic substance (for example, t-Boc, etc.), methyl vinyl benzoate, α-methylstyrene, and the like. Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, and the like.

In addition to the above compounds, (meth) acrylonitrile, a heterocyclic group substituted with a vinyl group (for example, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N -Vinylimidazole, vinyl caprolactone, etc. can also be used.

2-acrylamide-2-methylpropanesulfonic acid, monophosphate (2-acryloyloxyethyl ester), monophosphate (1-methyl-2-acryloyloxyethyl ester), and the like can also be used.

In addition to the above compounds, for example, vinyl monomers having functional groups such as urethane groups, urea groups, sulfonamide groups, phenol groups and imide groups can also be used. As a monomer which has such a urethane group or a urea group, it is possible to synthesize | combine suitably using the addition reaction of an isocyanate group, a hydroxyl group, or an amino group, for example. Specifically, addition reaction of 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 a primary or secondary amino group-containing monomer and a monoisocyanate It can synthesize | combine suitably by addition reaction or the like.

As a specific example of an isocyanate group containing monomer, the following compounds are mentioned, for example (R <^1> represents a hydrogen atom or a methyl group).

As a specific example of monoisocyanate, cyclohexyl isocyanate, n-butyl isocyanate, toluyl isocyanate, benzyl isocyanate, phenyl isocyanate, etc. are mentioned, for example.

As a specific example of a hydroxyl group containing monomer, the following compounds are mentioned, for example (R <^1> represents a hydrogen atom or a methyl group, n represents the 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 a substituent further containing fluoroethanol, Trifluoroethanol, methoxy ethanol, phenoxyethanol, chlorophenol, dichlorophenol, methoxyphenol, acetoxyphenol and the like.

As an example of a primary or secondary amino group containing monomer, vinylbenzylamine etc. are mentioned, for example.

Specific examples of the compound containing one primary or secondary amino group include alkylamines (methylamine, ethylamine, n-propylamine, i-propylamine, n-butylamine, sec-butylamine, t-butylamine, Hexylamine, 2-ethylhexylamine, decylamine, dodecylamine, octadecylamine, dimethylamine, diethylamine, dibutylamine, dioctylamine), cyclic alkylamines (cyclopentylamine, cyclohexylamine, etc.), Aralkylamines (benzylamine, phenethylamine, etc.), arylamines (aniline, toluylamine, xylylamine, naphthylamine, etc.), combinations thereof (such as N-methyl-N-benzylamine), and substituents The amine (trifluoroethylamine, hexafluoroisopropylamine, methoxyaniline, methoxypropylamine etc.) which contain further is mentioned.

1 type of said compounds may be used together and 2 or more types may be used together. Examples of other particularly preferred monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, styrene, chlorostyrene, and bromostyrene. And hydroxystyrene and the like.

Such a vinyl copolymer is obtained by copolymerizing the corresponding monomer, respectively by a well-known method according to a conventional method. For example, it is obtained using the method (solution polymerization method) which melt | dissolves these monomers in a suitable solvent, and adds a radical polymerization initiator to this, and superposes | polymerizes in solution. Moreover, you may superpose | polymerize by what is called an emulsion polymerization etc. in the state which disperse | distributed the said monomer in the aqueous medium.

As an example of the suitable solvent used by the solution polymerization method, it can select arbitrarily according to the solubility of the monomer to be used and the copolymer to produce | generate. 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, dimethyl Formamide, chloroform and toluene. You may use these solvent in mixture of 2 or more type. Moreover, as a radical polymerization initiator, azo compounds, such as 2,2'- azobis (isobutyronitrile) (AIBN), 2,2'- azobis- (2,4'- dimethylvaleronitrile), and benzoyl peroxide Peroxides, and persulfates, such as potassium persulfate and ammonium persulfate, etc. can be used.

As for the content rate of the repeating unit derived from the polymeric compound which has a carboxyl group in the vinyl copolymer obtained from these monomers, 5-50 mol% in each photosensitive layer of all the repeating units of a copolymer is preferable, More preferably, it is 10- 40 mol%, and 15-35 mol% are especially preferable. When the said content rate is less than 5 mol%, developability to an alkaline water may run short, and when it exceeds 50 mol%, the developing solution tolerance of a hardened part (image part) may run short.

Although the molecular weight of the binder which has a carboxyl group can be adjusted arbitrarily, 2000-30000 are preferable as a mass mean molecular weight for each photosensitive layer, and 4000-150000 are especially preferable. If the mass average molecular weight is less than 2000, the film strength tends to be insufficient, and stable production tends to be difficult. Moreover, when molecular weight exceeds 300000, there exists a tendency for developability to fall.

Moreover, as for the binder which has these carboxyl groups, each photosensitive layer may use 1 type, or may use 2 or more types of binder together. As an example in the case of using 2 or more types of binder together, 2 or more types of binder which consist of another copolymerization component, 2 or more types of binder of different mass mean molecular weight, 2 or more types of binder of different dispersion degree, etc. are mentioned.

In the binder having a carboxyl group, part or all of the carboxyl group may be neutralized with a basic substance. The binder may further use a resin having a different structure such as a polyester resin, a polyamide resin, a polyurethane resin, an epoxy resin, a polyvinyl alcohol, gelatin, or the like.

Moreover, as an example of a binder, resin etc. which are soluble in the alkali aqueous solution of Japanese Patent No. 2873889 etc. are mentioned.

Content of the binder in a photosensitive layer is 10-90 mass% normally in each photosensitive layer, Preferably it is 20-80 mass%, Especially preferably, it is 40-80 mass%. Even when using polyurethane resin and another binder together, it is preferable to make content of the polyurethane resin in the photosensitive layer into 10 mass% or more. In addition, in order to adjust sensitivity, adjustment, such as making content rate of the binder contained in a 2nd photosensitive layer lower than content rate of the binder contained in a 1st photosensitive layer (high content rate of a polymeric compound) within the said range. May be performed.

[Polymerizable Compound]

Although a polymeric compound (so-called monomer) is used for a photosensitive layer, it is especially preferable to use the monomer or oligomer (polyfunctional monomer, polyfunctional oligomer) containing two or more polymeric groups. As a polymerizable group, an ethylenically unsaturated bond (for example, a (meth) acryloyl group, a (meth) acrylamide group, a styryl group, vinyl groups, such as a vinyl ester and a vinyl ether, an allyl group, such as an allyl ether and an allyl ester, etc.) , Polymerizable cyclic ether groups (for example, epoxy groups, oxetane groups, and the like) and the like. Among these, ethylenically unsaturated bonds are preferable.

Examples of such polyfunctional monomers include esters of unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with aliphatic polyhydric alcohol compounds, unsaturated carboxylic acids, and polyvalent amines. Amides with compounds, and the like.

As a specific example of the ester monomer of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid, as (meth) acrylic acid ester, ethylene glycol di (meth) acrylate and polyethyleneglycol di (meth) acrylate whose number of ethylene groups are 2-18 (example) For example, diethyleneglycol 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, etc.), propylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate (for example, dipropylene having 2 to 18 propylene groups) Glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, dodecap Propylene glycol di (meth) acrylate), neopentyl glycol di (meth) acrylate, ethylene oxide modified neopentyl glycol di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, trimethylol ethane tri (meth) acrylate, 1,3- Propanedioldi (meth) acrylate, 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, tetramethylene glycoldi (Meth) acrylate, 1, 4- cyclohexanediol di (meth) acrylate, 1,2, 4- butane triol tri (meth) acrylate, 1, 5- pentanediol (meth) acrylate, pentaerythritol Di (meth) acrylate, pentaerythritol tree ( Ta) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, Sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate, dimethyloldicyclopentanedi (meth) acrylate, tricyclodecanedi (meth) acrylate, neopentyl glycoldi (meth) acrylate, neopentyl Di (meth) acrylates of alkylene glycol chains having at least one glycol-modified trimethylolpropanedi (meth) acrylate and an ethylene glycol chain / propylene glycol chain (for example, compounds described in WO 01/98832) Tri (meth) acrylic acid ester of trimethylolpropane with addition of ethylene oxide and / or propylene oxide, polybutylene Koldi (meth) acrylate and the like, glycerol di (meth) acrylate, glycerin tri (meth) acrylate, greater noldi silane (meth) acrylate.

Preferred examples of the above-mentioned (meth) acrylic acid esters include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and polypropylene glycol di ( Meth) acrylate, di (meth) acrylate of an 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, glycerin tri (meth) acrylate, diglycerindi (meth) acrylate, 1,3-propanedioldi (meth) acrylate, 1,2,4-butane triol tri (meth) acrylic Tri (meth) of trimethylolpropane added with hydrate, 1,4-cyclohexanediol di (meth) acrylate, 1,5-pentanediol (meth) acrylate, neopentyl glycol di (meth) acrylate, and ethylene oxide Acrylic esters; and the like.

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

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

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

Moreover, as an example of the amide derived from a polyvalent amine compound and unsaturated carboxylic acids, methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, 1, 6- hexamethylenebis (meth) acrylamide, octamethylenebis (meth) ) Acrylamide, diethylenetriamine tris (meth) acrylamide, diethylenetriaminebis (meth) acrylamide, and xylylenebis (meth) acrylamide.

2,2-bis [4- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] propane and 2,2-bis [4-((meth) acryloxyethoxy) further having a bisphenol skeleton 2,2-bis (4-((meth) acryloyloxypolyethoxy) phenyl) propane having a number of 2 to 20 phenyl] propane and an ethyleneoxy group 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) acryloyloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxydecaethoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloyloxypentadecaethoxy) phenyl) propane), 2,2-bis [4-((meth) acryloyloxypropoxy) phenyl] propane, with one phenolic OH group 2,2-bis (4-((meth) acryloyloxypolypropoxy) phenyl) propane having a number of substituted propyleneoxy groups of 2 to 20 Cotton, 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, 2,2 -Bis (4-((meth) acryloyloxypentadecapropoxy) phenyl) propane or the like) or a compound containing both a polyethylene oxide skeleton and a polypropylene oxide skeleton in the same molecule as the polyether moiety of these compounds And the like (for example, compounds described in WO 01/98832). These compounds can be obtained as BPE-200, BPE-500, BPE-1000 (made by Shin-Nakamura Kagaku Kogyo KK) etc., for example.

Moreover, the compound (2-isocyanate ethyl (meth) acrylate, (alpha), (alpha)-dimethyl-) which has an isocyanate group and a polymerization group with respect to the compound which has a hydroxyl group at the terminal obtained as bisphenol, an adduct, such as ethylene oxide and a propylene oxide, and a polyadditive Like the adduct of vinyl benzyl isocyanate etc., the polymeric compound which has a bisphenol skeleton and a urethane group can also be used.

In addition, novolak-type epoxy resins, butanediol-1,4-diglycidyl ether, cyclohexane dimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol digly Α to glycidyl group-containing compounds such as cydyl ether, hexanediol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol tetraglycidyl ether, bisphenol A diglycidyl ether, and glycerin triglycidyl ether The compound obtained by adding, (beta)-unsaturated carboxylic acid can also be used.

Moreover, the compound containing a polymeric group and a urethane group can also be used. Examples of such compounds include Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 5-50737, Japanese Patent Publication No. 7-7208, Japanese Patent Publication 2001-154346, Japanese Patent Publication 2001-356476 The polyisocyanate compound (for example, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate) described in the publication etc., and having two or more isocyanate groups in 1 molecule, for example. , Biphenyl or isocyanurate of phenylene diisocyanate, norbornene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diphenyl diisocyanate or diisocyanate thereof; Trimers, diisocyanates and trimethylolpropane, pentaerythritol and glycerin Polyfunctional alcohols such as these, or adducts with polyfunctional alcohols obtained such as ethylene oxide adducts thereof, and vinyl monomers containing hydroxyl groups in the molecule (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) acrylic Elate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, pentaerythritol tri (meth) acrylate The vinylurethane compound etc. which contain two or more polymerizable vinyl groups in 1 molecule obtained by adding etc. are mentioned. Also, isocyanurate rings such as tri ((meth) acryloyloxyethyl) isocyanurate, di (meth) acrylated isocyanurate, tri (meth) acrylate of ethylene oxide-modified isocyanuric acid, etc. The compound which has is also available.

Furthermore, polyester acrylates and polyester (meth) acrylate oligomers as described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490; Epoxy compounds (novolak type epoxy resin, butanediol-1,4-diglycidyl ether, cyclohexane dimethanol 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 epoxy methacrylates to which (meth) acrylic acid was reacted. Polyfunctional acrylate and methacrylate can be mentioned. Examples thereof also include phthalic acid, trimellitic acid, and esterified products obtained from vinyl monomers containing hydroxyl groups in the above molecules. Moreover, the thing introduce | transduced as a photocurable monomer and oligomer can also be used by Japanese adhesion association vol.20, No. 7, page 300-308 (1984).

Furthermore, allyl ester (for example, diallyl phthalate, diallyl diallyl, diallyl malonic acid, diallyl phthalate, triallyl trimellitic acid, diallyl, benzene disulfonic acid diallyl, triallyl isocyanurate, etc.); And diallylamide (for example, diallyl acetamide, etc.) can also be used.

As the polymerizable compound, cationic polymerizable divinyl ethers (for example, butanediol-1,4-divinyl ether, cyclohexanedimethanoldivinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, di Propylene glycol divinyl ether, hexanediol divinyl ether, trimethylol propane trivinyl ether, pentaerythritol tetravinyl ether, bisphenol A divinyl ether, glycerin trivinyl ether, etc.), epoxy compound (novolak type epoxy resin, butanediol-1) , 4-diglycidyl ether, cyclohexane dimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl Ether, trimethylolpropanetriglycidyl ether, pentaerythritol tetraglycidyl ether, bisphenol A diglycidyl ether, glycerin triglycidyl And the like, and oxetanes (for example, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene) can also be used. In addition, as an epoxy compound and oxetane, the compound of WO 01/22165 can also be used.

Examples of vinyl esters include divinyl succinate, divinyl adipate, divinyl phthalate, divinyl terephthalate, divinylbenzene-1,3-disulfonate, divinylbutane-1,4-disulfonate, and the like. It is available.

As an example of a styrene compound, divinyl benzene, 4-allyl styrene, 4-isopropene styrene, etc. can be mentioned.

Moreover, as compounds other than the said compound, N- (beta) -hydroxyethyl- (beta)-(methacrylamide) ethyl acrylate, N, N-bis ((beta) -methacryloxyethyl) acrylamide, allyl methacrylate, etc. are mentioned. And compounds having two or more other ethylenically unsaturated double bonds may also be enumerated as the compounds suitably used in the present invention.

These polyfunctional monomers and oligomers can be used individually or in combination of 2 or more types.

Moreover, the polymerizable compound (monofunctional monomer) which contains one polymeric group in a molecule | numerator can also be used together as needed. As an example of a monofunctional monomer, the compound illustrated as a raw material of the above-mentioned binder, mono ((meth) acryloyloxyalkyl ester) mono (halohydroxyalkyl) of the bibasic as disclosed in Unexamined-Japanese-Patent No. 6-236031. Monofunctional monomers such as esters (e.g., γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl-o-phthalate, etc.), and Japanese Patent Nos. 2744643 and WO 01/52529. And the compounds described in JP 2548016 A and the like.

The content of the monomer of the photosensitive layer is generally in the range of 5 to 90% by mass in each of the photosensitive layers, preferably in the range of 15 to 60% by mass, and particularly preferably in the range of 20 to 50% by mass. If the content of the monomer is less than the above range, the strength of the tent film decreases, and if the content of the monomer is large, the edge fusion during the storage (the exudation failure from the roll end) tends to deteriorate. Moreover, content of the polyfunctional monomer containing two or more polymerizable groups among all the monomers is generally the range of 5-100 mass%, Preferably it is the range of 20-100 mass%, More preferably, it is 40-100 mass Range of%. In addition, in order to adjust sensitivity, you may make adjustments, such as making the monomer content rate of a 2nd photosensitive layer high within the said range.

[Photopolymerization Initiator]

As a photoinitiator used for the photosensitive transfer sheet of this invention, all the compounds which have the ability to start superposition | polymerization of the monomer component mentioned above can be used, and it can use suitably especially if it has photosensitivity with respect to visible light from an ultraviolet range. . It is preferable that a photoinitiator contains at least 1 sort (s) of component which has a molecular extinction coefficient of at least about 50 in the range of about 300-800 nm (more preferably 330-500 nm). The photopolymerization initiator may further be an activator which generates any action with a photoexcited sensitizer and generates active radicals, or may be an initiator that initiates cationic polymerization depending on the type of monomer.

As a photoinitiator used suitably for a photosensitive layer, For example, Halogenated hydrocarbon derivative (For example, having triazine skeleton, Having oxadiazole skeleton), Hexaaryl biimidazole, Oxime derivative, Organic peroxide, Thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers and the like. Among them, the use of halogenated hydrocarbons, oxime derivatives, hexaarylbiimidazoles, and ketone compounds having a triazine skeleton, among others, is a viewpoint of the sensitivity, the storage properties, and the adhesion between the photosensitive layer and the substrate for forming a printed wiring board. Preferred at

Examples of the halogenated hydrocarbon compound having a triazine skeleton include the following compounds.

Wakabayashi et al., Compounds described by Bull. Chem. Soc. Japan, 42, 2924 (1969), for example 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-crophenyl) -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) -1,3,5-triazine, and 2- (α, α, β -Trichloroethyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

Compounds described in British Patent 1388492, for example 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4, 6-bis (trichloromethyl) -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 Japanese Patent Application Laid-Open No. 53-133428, for example 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -1,3,5-tri Azine, 2- (4-ethoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl) -Naphtho-1-yl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphtho-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 German Patent 3337024, 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-vinylene Phenyl) -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-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (4-benzofuran -2-vinylene phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

29, 1527 (1964) by FCSchaefer et al., 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.

Japanese Patent Application Laid-Open No. 62-58241, 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-ethyl Phenylethynyl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

Japanese Patent Application Laid-Open No. 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 (trichloro Methyl) -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 described in JP-A-5-34920 , 5-triazine, trihalomethyl-s-triazine compound described in US Pat. No. 4239850, also 2,4,6-tris (trichloromethyl) -s-triazine, 2- (4 -Chlorophenyl) -4,6-bis (tribromomethyl) -s-triazine and the like.

Also listed are compounds having an oxadiazole skeleton described in US Pat. No. 4212976 and the like. Examples of the compound having an oxadiazole skeleton include 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole and 2-trichloromethyl-5- (4-chlorophenyl) -1,3 , 4-oxadiazole, 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-trichloro Rhomethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2 -Trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tribromomethyl-5-styryl-1,3,4-oxadiazole and the like This is listed.

As an oxime derivative used preferably by this invention, the compound represented by the following general formula can be mentioned.

As hexaaryl biimidazole which can be used for this invention, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole and 2,2'-bis (2 -Fluorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'-tetraphenylbiimi Dazole, 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) ratio Imidazole, 2,2'-bis (4-methoxyphenyl) -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, 2,2'-bis (2-trifluoromethylphenyl) -4,4', 5,5'-tetraphenylbiimi Dazoles, compounds described in WO 01/52529, and the like.

Said biimidazoles are easily synthesized by, for example, the method disclosed in Bull. Chem. Soc. Japan, 33,565 (1960), and J. Org. Chem, 36 (16) 2262 (1971). can do.

Examples of the ketone compounds include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone and 4-bromobenzophenone. , 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid or tetramethyl ester thereof, 4,4'-bis (dialkylamino) benzophenones (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-butyl Anthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro-thioxanthone, 2,4-diethyl thioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinofe ) -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 (for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), ah Cridonone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone and the like.

In addition, polyhalogen compounds such as acridine derivatives (e.g., 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane), N-phenylglycine, and the like (e.g., For example, carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, etc.), coumarins (for example, 3- (2-benzoproyl) -7-diethylaminocoumarin, 3- (2) -Benzoproyl) -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-proyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy 3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, and the like. Japanese Patent Laid-Open No. 5-19475, Japanese Patent Laid-Open No. 7-271028, Japanese Patent Laid-Open No. 2002-363206, Japanese Patent Laid-Open 2002-363207, Japanese Patent Laid-Open 2002-363208, Japanese Patent Laid-Open No. 2002-363209 Coumarin compounds described in the above, and the like, amines (for example, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid n-butyl, 4-dimethylaminobenzoic acid phenethyl, 4-dimethylaminobenzoic acid 2-phthalimideethyl , 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, tetra Ribbenzylamine, dibenzylphenylamine, N-methyl-N-phenylbenzylamine, 4-bromine-N, N-dimethylaniline, tridodecylamine, aminofluorans (ODB, ODBII, etc.), crystal violet lactone, Leuco crystal violets, etc.), acylphosphine oxides (for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4, 4-trimethyl-pentylphenylphosphine oxide, LucirinTPO and the like), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3) -(1H-pyrrole-1-yl) -phenyl) titanium, -5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.), Japanese Patent Application Laid-Open No. 53- 133428, Japanese Patent Application Laid-Open No. 57-1819, Japanese Patent Application Laid-Open No. 57-6096, and the compounds disclosed in the specification of US Patent No. 3615455.

Aromatics substituted with α-hydrocarbons as described in the US Pat. No. 2,367,660 bisinal polyketaldonyl compounds, the acyloinether compounds described in US 2448828, and US Pat. Triarylsulfonium salts, such as the acyloin compound, the polynuclear quinone compound described in US Patent No. 3046127 and the Japanese Patent No. 2951758, the organoboron compound described in Japanese Patent Application Laid-Open No. 2002-229194, and other exemplary radical generators Phosphonium salt compounds (effective as cationic polymerization initiators) such as (salts with hexafluoroantimony or hexafluorophosphate), (phenylthiophenyl) diphenylsulfonium salts, onium salt compounds described in WO 01/71428, and the like. Can also be used.

A photoinitiator can be used combining one or two or more. As such a combination, for example, the combination of hexaarylbiimidazole and 4-amino ketones described in US Pat. No. 3,354,67, the benzothiazole compound described in JP-A-51-48516 and trihalomethyl- combinations of s-triazine compounds and the like. Combination of aromatic ketone compounds such as thioxanthone and hydrogen donors (e.g., dialkylamino-containing compounds, phenol compounds, etc.), combination of hexaarylbiimidazole and titanocene, coumarins, titanocene and phenylglycine Combinations can also be used.

As for the usage-amount of a photoinitiator, the range of 0.1-30 mass% is common with respect to all the components of a photosensitive layer in each photosensitive layer generally, Preferably it is the range of 0.5-20 mass%, Especially preferably, it is 0.5-15 It is the range of mass%. In addition, when adjusting the sensitivity difference of each photosensitive layer by content of a photoinitiator, what is necessary is just to make the quantity of the photoinitiator contained in a 2nd photosensitive layer more than the quantity of the photoinitiator contained in a 1st photosensitive layer. It is preferable to make content of the photoinitiator of a 2nd photosensitive layer into the quantity of 1.5-100 times with respect to content of the photoinitiator of a 1st photosensitive layer, Furthermore, the quantity of 1.8 times-50 times is preferable, Especially 2-20 times It is preferable to make it into quantity.

[Sensitizer]

A sensitizer can be added for the purpose of adjusting the sensitivity and the photosensitive wavelength in exposure of each photosensitive layer. In the case of using visible light, ultraviolet light or visible light laser as exposure light (active energy ray), the sensitizer is excited by the active energy ray, and other substances (e.g., radical generator, acid generator, etc.) ) (For example, energy transfer, electron transfer, etc.), and useful groups such as radicals and acids can be generated.

As a sensitizer, well-known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, fluorescein, eosin, erythrosin, rhodamine B, rose bengal) , Cyanines (e.g., Indian carbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (e.g. merocyanine, carbomerocyanine), thiazines (e.g. , Thionine, methylene blue, toluidine blue), acridines (e.g., acridine orange, chloroflavin, acriflavin), anthraquinones (e.g., anthraquinones), squariases (e.g., For example, squaria), acridones (for example, acridon, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, etc.), coumarins (For example 3- (2-benzoproyl) -7-diethylaminocoumarin, 3- (2-benzoproyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethyl Aminocoumarin , 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-propyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin and the like JP-A 5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-JP And coumarin compounds described in each publication such as 2002-363209).

As a combination of a polymerization initiator and a sensitizer, the electron transfer type | system | group initiator described in Unexamined-Japanese-Patent No. 2001-305734, (1) electron donating type initiator and sensitizing dye, (2) electron accepting type initiator and sensitizing dye, (3) an electron donor type initiator, a sensitizing dye, and an electron accepting type initiator (three circle clock)] etc. are mentioned.

Each of the first photosensitive layer and the second photosensitive layer may contain a sensitizer. The addition amount of a sensitizer is generally in the range of 0.05-30 mass% with respect to the all components of the photosensitive resin composition, Preferably it is the range of 0.1-20 mass%, Especially preferably, the range of 0.2-10 mass% to be. When there is much addition amount of a sensitizer, it precipitates at the time of storage from a photosensitive layer, and when too little, the sensitivity to an active energy ray will fall, an exposure process may take time, and productivity may fall.

When adjusting the sensitivity difference of each photosensitive layer with a sensitizer, what is necessary is just to make the quantity of the sensitizer contained in a 2nd photosensitive layer more than the quantity of the sensitizer contained in a 1st photosensitive layer. The sensitizer content of the second photosensitive layer is preferably 1.5 to 100 times the amount, more preferably 1.8 to 50 times the amount, more preferably 2 to 20 times the content of the sensitizer of the first photosensitive layer. It is especially preferable to make it into a quantity. The first photosensitive layer may be adjusted such that it does not contain a sensitizer.

[Other Ingredients]

If necessary, the photosensitive layer may be a thermal polymerization inhibitor, a plasticizer, a coloring agent, a coloring agent, an adhesion promoter to the surface of the substrate, and other preparations (for example, pigments, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, and peelings). Accelerators, antioxidants, fragrances, thermal crosslinking agents, surface tension modifiers, chain transfer agents, etc.) may be used in combination, thereby controlling the properties of stability, photographic properties, printability, film properties, etc., of the intended photosensitive transfer sheet. have. Said component can be added to both a 1st photosensitive layer and a 2nd photosensitive layer, The addition amount may be determined according to the objective, and the addition amount to each photosensitive layer may be same or different.

[Thermal polymerization inhibitor]

You may add a thermal-polymerization inhibitor in order to prevent thermal superposition | polymerization or time-lapse superposition | polymerization of the polymeric compound of a photosensitive layer. Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone and 4-methoxy-2-hydride. Roxybenzophenone, cuprous chloride, phenothiazine, chloranyl, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2'-methylenebis (4-methyl- 6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, nitroso compound and Al Chelates and the like.

It is preferable that the addition amount of a thermal polymerization inhibitor exists in the range of 0.001-5 mass% with respect to the polymeric compound of a photosensitive layer, More preferably, it is the range of 0.005-2 mass%, Especially preferably, it is 0.01-1 mass Range of%. When the amount of the thermal polymerization inhibitor added exceeds this range, the sensitivity to the active energy ray tends to decrease, and when it exceeds this range, the stability during storage tends to decrease.

[Plasticizer]

You may add a plasticizer in order to control the film physical property (flexibility) of a photosensitive layer. Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butylbenzyl phthalate, diisodecyl phthalate, diphenyl phthalate and diallyl phthalate. Phthalic acid esters such as octylcaprylphthalate; Glycol esters such as triethylene glycol diacetate, tetraethylene glycol diacetate, dimethyl glycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate and triethylene glycol dicarblic acid ester; Phosphoric acid esters such as tricresyl phosphate and triphenyl phosphate; Amides such as 4-toluenesulfonamide, benzenesulfonamide, N-n-butylbenzenesulfonamide and N-n-butylacetamide; Aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioctyl sebacate, dioctyl azelate and dibutyl maleate; Glycols such as polyethylene glycol and polypropylene glycol, such as triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, and 4,5-diepoxycyclohexane-1,2-dicarboxylic acid dioctyl Listed.

It is preferable that the addition amount of a plasticizer exists in the range of 0.1-50 mass% with respect to the all components of a photosensitive layer, More preferably, it is the range of 0.5-40 mass%, Especially preferably, it is the range of 1-30 mass%.

[Coloring agent]

A coloring agent may be added in order to give a visible image (printing function) to the photosensitive layer after exposure. As a coloring agent, for example, tris (4-dimethylaminophenyl) methane (leuco crystal violet), tris (4-diethylaminophenyl) methane, tris (4-dimethylamino-2-methylphenyl) methane, tris (4 -Diethylamino-2-methylphenyl) methane, bis (4-dibutylaminophenyl)-[4- (2-cyanoethyl) methylaminophenyl] methane, bis (4-dimethylaminophenyl) -2-quinolyl Aminotriaryl methanes such as methane and tris (4-dipropylaminophenyl) methane; Aminoxanthines such as 3,6-bis (dimethylamino) -9-phenylxanthine and 3-amino-6-dimethylamino-2-methyl-9- (2-chlorophenyl) xanthine; Aminothioxanthenes such as 3,6-bis (diethylamino) -9- (2-ethoxycarbonylphenyl) thioxanthene and 3,6-bis (dimethylamino) thioxanthene; 3,6-bis (diethylamino) -9,10-dihydro-9-phenylacridine, 3,6-bis (benzylamino) -9,10-dihydro-9-methylacridine Amino-9,10-dihydroacridines; Amino phenoxazines such as 3,7-bis (diethylamino) phenoxazine; Aminophenothiazines such as 3,7-bis (ethylamino) phenothiazine; Aminodihydrophenazines such as 3,7-bis (diethylamino) -5-hexyl-5,10-dihydrophenazine; Aminophenylmethanes such as bis (4-dimethylaminophenyl) anilinomethane; Aminohydro cinnamic acids such as 4-amino-4'-dimethylaminodiphenylamine and 4-amino-α, β-dicyanohydrocinnamic acid methyl ester; Hydrazines such as 1- (2-naphthyl) -2-phenylhydrazine; Amino-2,3-dihydroanthraquinones of 1,4-bis (ethylamino) -2,3-dihydroanthraquinones; Phenethylanilines such as N, N-diethyl-4-phenethylaniline; Acyl derivatives of leuco pigments containing basic NH such as 10-acetyl-3,7-bis (dimethylamino) phenothiazine; Leuco-type compounds which do not have oxidizable hydrogen, such as tris (4-diethylamino-2-tolyl) ethoxycarbonylmethane, but which can be oxidized to a coloring compound; Leuco indigo dyes; Organic amines that can be oxidized to color forms such as those described in US Pat. Nos. 3,042,515 and 3,042,517 (e.g., 4,4'-ethylenediamine, diphenylamine, N, N-dimethylaniline, 4,4 ') -Methylenediaminetriphenylamine, N-vinylcarbazole). Particularly preferred are triaryl methane compounds such as leuco crystal violet.

Moreover, combining with a halogen compound is known for the purpose of color-developing these leuco bodies. Examples of halogen compounds include halogenated hydrocarbons (e.g. carbon tetrabromide, iodide, ethylene bromide, methylene bromide, amyl bromide, isoamyl bromide, amyl iodide, isobutyl bromide, butyl iodide, brominated diphenylmethyl, 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 and the like); Halogenated alcohol compounds (e.g. 2,2,2-trichloroethanol, tribromoethanol, 1,3-dichloro-2-propanol, 1,1,1-trichloro-2-propanol, di (iodinehexa) Methylene) aminoisopropanol, tribromo-t-butyl alcohol, 2,2,3-trichlorobutane-1,4-diol and the like); Halogenated carbonyl compounds (e.g., 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-bromoethylmethyl ether, 2-bromoethylethyl ether, di (2-bromoethyl) ether, 1,2-dichloroethylethyl ether, etc.); Halogenated ester compounds (e.g., bromoethyl acetate, trichloroacetic acid, trichloroacetic acid trichloroethyl, homopolymers and copolymers of 2,3-dibromopropylacrylate, trichloroethyl dibromopropionate, α, β-ethyl dichloroacrylate and the like); Halogenated amide compounds (e.g., chloroacetamide, bromoacetamide, dichloroacetamide, trichloroacetamide, tribromoacetamide, trichloroethyltrichloroacetamide, 2-bromoisopropionamide, 2, 2,2-trichloropropionamide, N-chlorosuccinamide, N-bromosuccinimide and the like); Compounds having sulfur or phosphorus (for example, tribromomethylphenylsulfone, 4-nitrophenyltribromomethylsulfone, 4-chlorophenyltribromomethylsulfone, tris (2,3-dibromopropyl) phosphate, etc.) ), 2,4-bis (trichloromethyl) 6-phenyltriazole, and the like. Among the organic halogen compounds, halides having two or more halogen atoms bonded to the same carbon atom are preferable, particularly preferably halides having three halogen atoms on one carbon atom. An organic halogen compound may be used independently and may be used together 2 or more types. Among these, especially preferable organic halogen compounds are tribromomethylphenyl sulfone and 2, 4-bis (trichloromethyl) -6-phenyltriazole.

As for the addition amount of a coloring agent, the range of 0.01-20 mass% is preferable with respect to the all components of the photosensitive layer, More preferably, it is the range of 0.05-10 mass%, Especially preferably, it is the range of 0.1-5 mass%. Moreover, the range of 0.001-5 mass% is common with respect to the whole component of the photosensitive layer, and, as for the quantity of a halogen compound, 0.005-1 mass% is preferable.

[dyes]

Dye can be used for the photosensitive layer for the purpose of coloring the photosensitive resin composition or providing storage stability for the improvement of handleability. Examples of preferred dyes include brilliant green (e.g. sulfate thereof), eosin, ethyl violet, erythrosin B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyl triazine, Alizarin Red S, thymolphthalein, methylviolet 2B, quinaldine red, rose bengal, methyl-yellow, thymolsulfophthalein, xylenol blue, methyl orange, orange IV, diphenyltyrocarbazone, 2, 7-dichlorofluorescein, paramethyl red, Congo red, benzofurfurin 4B, α-naphthyl-red, nile blue A, phenacetarin, methyl violet, malachite green, parafuxine, oil blue # 603 (orient Kagaku Kogyo Co., Ltd.), Rhodamine B, and Rhodamine 6G, Victoria Pure Blue BOH, and the like. The counter anion of the cationic dye may be a residue of an organic acid or an inorganic acid, and examples thereof include residues (anions) such as bromic acid, iodic acid, sulfuric acid, phosphoric acid, oxalic acid, methanesulfonic acid and toluenesulfonic acid. Preferred dyes are cationic dyes, for example malachite green oxalate, malachite green sulfate and the like.

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

[Adhesive Promoter]

In order to improve the adhesiveness between each layer, or the adhesiveness of the photosensitive transfer sheet | seat and gas, a well-known so-called adhesion promoter can be used for each layer.

As an adhesion promoter, the adhesion promoter described in Unexamined-Japanese-Patent No. 5-11439, Unexamined-Japanese-Patent No. 5-341532, Unexamined-Japanese-Patent No. 6-43638, etc. can be used preferably. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl- Triazole-2-thione, 3-morpholinomethyl-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.

The preferable addition amount of an adhesion promoter exists in the range of 0.001 mass%-20 mass% with respect to the all components of a photosensitive layer. More preferably, it is the range of 0.01-10 mass%, Especially preferably, it is the range of 0.1 mass%-5 mass%.

The photosensitive layer is, for example, an organic sulfur compound, a peroxide, a redox-based compound, an azo and a diazo compound, a photoreductive dye, and an organic halogen compound as described in Chapter 5 of Light Sensitive Systems, J. Co., Ltd. And the like may be contained. Examples of the organic sulfur compound include di-n-butyldisulfide, dibenzyldisulfide, 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, thiophenol, ethyltrichloromethanesulfonate, 2-mercaptobenzimidazole This may be listed. Examples of the peroxide include di-t-butyl peroxide, benzoyl peroxide and methyl ethyl ketone peroxide. The redox compound consists of a combination of a peroxide and a reducing agent, and ferrous ions and persulfate ions, ferric ions and peroxides and the like can be enumerated. As azo and diazo compounds, the diazonium of (alpha), (alpha) '-azobisiributyronitrile, 2-azobis-2-methylbutyronitrile, 4-aminodiphenylamine can be mentioned. Examples of the photoreducing pigments include rose bengal, erythrosine, eosin, acriflavin, lipoflavin and thionine.

[Surfactants]

In order to improve the planar stain which arises at the time of manufacturing the photosensitive transfer sheet, a well-known surfactant can be added. As an example of surfactant, it can select suitably from anionic and cationic surfactant, nonionic surfactant, amphoteric surfactant, fluorine-containing surfactant, etc. 0.001-10 mass% is preferable with respect to solid content of the photosensitive resin composition, and when the addition amount is less than 0.001 mass%, the effect of planar improvement is not acquired, and when it exceeds 10 mass%, the problem that adhesiveness falls easily occurs. As fluorine-based surfactant, acrylate or meta having a fluoro aliphatic group containing 40 mass% or more of fluorine atoms in the carbon chain 3 to 20 and the hydrogen atoms bonded to at least three carbon atoms by counting from the unbonded ends are fluorine-substituted. Polymeric surfactants having acrylate as a copolymerization component are also preferable.

[Barrier Floor]

In the photosensitive transfer sheet or the photosensitive laminate of the present invention, a barrier layer is preferably disposed between the first photosensitive layer and the second photosensitive layer. The barrier layer has a role of preventing or inhibiting the migration of substances contained in the photosensitive layer, the support and the protective film, the prevention of migration, and external influences such as oxygen and humidity. For example, provision of a barrier layer has the effect of preventing the component of each photosensitive layer from moving to another layer, and changing a sensitivity and a film | membrane physical property.

It is preferable that a barrier layer contains resin, and it is preferable to contain resin as a main component which shows affinity with respect to water or the lower alcohol of 1-4 carbon atoms. Affinity means having emulsification, dispersion | distribution, swelling, partial dissolution, and hygroscopicity with respect to the said solvent. Moreover, it is preferable that a barrier layer contains soluble resin as a main component with respect to water or the lower alcohol of 1-4 carbon atoms.

Although the same binder as a photosensitive layer may be used for manufacture of said barrier layer, it is preferable that it is a layer which consists of binders different from this. As such a polymer, for example, various alcohol soluble, water soluble polymers, alcohol dispersibility, water dispersibility, emulsifying or alkali soluble polymers can be used, and examples thereof include polyvinyl alcohol (modified polyvinyl alcohols). ), Polyvinylpyrrolidone, water-soluble polyamide, gelatin, cellulose and the like and derivatives thereof. These polymers may be used independently and may use 2 or more types together. Moreover, you may add various polymers, such as an acryl-type polymer, an amide type polymer, and an ester type polymer, in the range which does not impair water solubility and alkali water solubility. As a barrier layer, the compound used for the thermoplastic resin and intermediate layer of patent 2794242 can also be used.

[Production of Photosensitive Transfer Sheet]

The photosensitive transfer sheet of this invention can be manufactured as follows, for example.

First, the above various materials are dissolved, emulsified or dispersed in water or a solvent to prepare a first photosensitive resin composition solution for forming a first photosensitive layer and a second photosensitive resin composition solution for forming a second photosensitive layer, respectively. . Moreover, when it has a barrier layer, the solution for formation is prepared.

As a solvent of a 1st photosensitive resin composition solution and a 2nd photosensitive resin composition solution, For example, Alcohol, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, n-hexanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diisobutyl ketone; Esters such as ethyl acetate, butyl acetate, n-amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, and methoxypropyl acetate; Aromatic hydrocarbons such as toluene, xylene, benzene and ethylbenzene; Halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride and monochlorobenzene; Ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and 1-methoxy-2-propanol; Dimethyl formamide, dimethyl acetamide, dimethyl sulfooxide, sulfolane, etc. can be used, These may be used in mixture. You may add a well-known surfactant to a 1st photosensitive resin composition solution and a 2nd photosensitive resin composition solution.

The coating solvent similar to the photosensitive layer may be used for the solvent of the polymer solution for barrier layer formation, and water or the mixed solvent of water and a solvent can be used. As the solvent, the above hydrophilic solvents such as alcohols such as methanol, ethanol, n-propanol, isopropanol and n-butanol can be used. The use of 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. When it has a barrier layer, the coating liquid for barrier layer formation is apply | coated and dried on a 1st photosensitive layer. The 2nd photosensitive layer is formed by apply | coating and drying a 2nd photosensitive resin composition solution on it. Application | coating at the time of lamination | stacking may be apply | coating sequentially as mentioned above, and may apply | coat in middle layer simultaneously. The coating method of the photosensitive resin composition solution is not specifically limited, For example, the spray method, the roll coating method, the rotary coating method, the slit coat method, the extrusion coating method, the curtain coating method, the die coating method, the gravure coating method, the wire bar Various methods, such as a coating method and the knife coat method, can be employ | adopted. As conditions of drying, although it changes also with each component, a kind of solvent, a use ratio, etc., it is about 30 to 15 minutes normally at the temperature of 60-110 degreeC.

Even when there are more than two photosensitive layers, a predetermined photosensitive transfer sheet can be manufactured by repeating the same operation. By making two or more photosensitive layers, it is also possible to make the total sum of the thickness of a photosensitive layer into the range of 10 micrometers-1 mm.

[Support and Protective Film]

It is preferable that a support body can peel a photosensitive layer, that light transmittance is favorable and that surface smoothness is good. The support is made of synthetic resin and is preferably 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, polyvinyl alcohol, Polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride-vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, cellulose film, nylon film, etc. Plastic films can be enumerated. Moreover, the composite material which consists of two or more of these can also be used. Among these, polyethylene terephthalate is especially preferable. 2-150 micrometers is preferable, as for the thickness of a support body, 5-100 micrometers is more preferable, 8-50 micrometers is especially preferable. The support is preferably a long support. Although the length of the elongate support body used when manufacturing the photosensitive transfer sheet of this invention may be arbitrarily determined, For example, the thing of the length of 10m-20000m can be used.

In the photosensitive transfer sheet of the present invention, a protective film may be disposed on the second photosensitive layer. Examples of the protective film may include those used for the support, 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. In that case, it is necessary to make the adhesive force A of a photosensitive layer and a support body, and the adhesive force B of a photosensitive layer and a protective film become a relationship of adhesive force (A)> adhesive force (B). Examples of the combination of the support / protective film may include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. Moreover, by surface-treating at least one of a support body and a protective film, the above relationship of adhesive force can be satisfied. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, the coating of the undercoat layer, the corona discharge treatment, the flame treatment, the ultraviolet irradiation treatment, the high frequency irradiation treatment, the glow discharge irradiation treatment, the active plasma irradiation Treatment, laser beam irradiation treatment and the like can be enumerated. In addition, the coefficient of static friction of the support and the protective film is also important. As for these static friction coefficients, 0.3-1.4 are preferable and 0.5-1.2 are especially preferable. If it is less than 0.3, it slips too much, and when it is set as a roll, winding shift arises. Moreover, when exceeding 1.4, it will become difficult to wind to a favorable roll shape.

The photosensitive transfer sheet of the present invention is wound, for example, in a cylindrical core, wound in a long shape in a roll shape, and stored. What is necessary is just to determine the length of this elongate body arbitrarily, for example, you may select in the range of 10m to 20000m. The slitting process is easy to be used by the user, and may be long and roll-shaped in the range of 100 m to 1000 m. In this case, the support is preferably wound up to the outermost side. The roll-shaped photosensitive transfer sheet may be slitted in a sheet form. In storage, 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 to use a material having low moisture permeability for packing. desirable.

You may surface-treat a protective film. Surface treatment is performed in order to adjust the adhesiveness of a protective film and a photosensitive layer. For example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, and polyvinyl alcohol is formed on the surface of the protective film. Formation of an undercoat layer is generally performed by apply | coating the coating liquid of the said polymer to the surface of a protective film, and then drying at 30-150 degreeC (especially 50-120 degreeC) for 1 to 30 minutes. In addition to the photosensitive layer, barrier layer, support, and protective film, a layer such as a cushion layer, a peeling layer, an adhesive layer, a light absorbing layer, a surface protective layer, or the like may be provided.

[gas]

As the substrate for transferring the photosensitive transfer sheet of the present invention, it can be arbitrarily selected from those having high surface smoothness to those having uneven surfaces. Preferably, a plate-shaped gas, a so-called substrate, is used. Specifically, the board | substrate for manufacturing a well-known printed wiring board, a glass plate (such as a soda glass plate), a synthetic resin film, paper, a metal plate, etc. are mentioned.

A second photosensitive layer composed of a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator on a substrate, and a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator, A first photosensitive layer exhibiting a photosensitivity lower than the photosensitivity is formed in this order to form a photosensitive laminate. Moreover, it is preferable to form the photosensitive laminated body by which the barrier layer is arrange | positioned between the said 1st photosensitive layer and a 2nd photosensitive layer.

The photosensitive transfer sheet of the present invention is widely used as a display member such as a printed wiring board, a color filter, a pillar material, a rib material, a spacer, a partition wall, various image forming materials such as holograms, micromachines, proofs, and pattern forming materials. It is possible. Among these, application to a printed wiring board and a display member is preferable, and application to a printed wiring board is especially preferable.

[Pattern Forming Method]

The photosensitive transfer sheet of this invention is a process of obtaining the laminated body by (1) laminating | stacking on the board | substrate in the positional relationship whose 2nd photosensitive layer becomes a board | substrate side, and (2) from the side of the 1st photosensitive layer of a laminated body. Irradiating the positive image pattern and curing the first photosensitive layer and the second photosensitive layer of the region subjected to the light irradiation together; (3) removing the support from the laminated body; and (4) the laminated body. To a region in which the cured resin is formed by curing the first photosensitive layer and the second photosensitive layer together on a substrate, and a region in which the cured resin does not exist, which includes developing a film and removing an uncured portion in the laminate. It is possible to form a predetermined pattern by the method of forming the configured image pattern.

Moreover, the photosensitive transfer sheet of this invention is a process of laminating | stacking on the board | substrate in the positional relationship whose 2nd photosensitive layer becomes a board | substrate side, and obtaining a laminated body, (2) The side of the 1st photosensitive layer of a laminated body. From the first photosensitive layer and the second photosensitive layer of the region which are irradiated with an image pattern that defines a region for irradiating light of irradiation energy amounts of at least two levels different from each other, and has received a relatively large amount of light irradiation energy. Curing together, and curing the second photosensitive layer in the region subjected to light irradiation with a relatively small amount of light irradiation energy, (3) removing the support from the laminate, and (4) developing the laminate, A region in which a resin formed by curing the first photosensitive layer and a second photosensitive layer together on a substrate, including a step of removing an uncured portion in the laminate, and a region in which a resin formed by curing the second photosensitive layer exist And hardening By a method for forming an image pattern composed of a land area that does not exist, it is also possible to form a predetermined pattern.

However, in the above method, the step of removing the support from the laminate of (3) may be performed between step (1) and step (2) instead of performing between step (2) and step (4). do.

As a light source for light irradiation in the step (2), when light irradiation is carried out through the support, electromagnetic waves for transmitting the support and activating the photopolymerization initiator and the sensitizer used, the wavelength is 300 to 1500 nm, preferably A light source for generating visible light from ultraviolet rays in the range of 320 to 800 nm, particularly preferably a light source in the range of 330 nm to 650 nm is used. For example, well-known light sources, such as fluorescent tubes, such as a (ultra) high pressure mercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, and a copier, LED, a semiconductor laser, can be used. In addition, you may use an electron beam or X-rays. Moreover, even when irradiating light after peeling a support body, the same light source can be used. Among them, light irradiation is preferably performed by laser light irradiation, the wavelength of the laser is preferably in the range of 200 to 1500 nm, further preferably in the range of 300 to 800 nm, and particularly in the range of 370 nm to 650 nm. Preferably, the range of 400 nm-450 nm is the most preferable.

[Manufacturing Method of Printed Wiring Board]

The photosensitive transfer sheet of this invention can be used suitably for manufacture of a printed wiring board, especially the manufacture of a printed wiring board which has hole parts, such as a through hole or a via hole.

The photosensitive transfer sheet of the present invention is (1) a step of laminating the second photosensitive layer in a positional relationship in which the second photosensitive layer is on the substrate side to obtain a laminate, and (2) predetermined from the side of the first photosensitive layer of the laminate. Irradiating light on the wiring pattern and curing the first photosensitive layer and the second photosensitive layer in the region subjected to the light irradiation, (3) removing the support from the laminated body, and (4) the laminated body. And the surface of the substrate and the area covered with the cured resin formed by curing the first photosensitive layer and the second photosensitive layer together on a printed wiring board forming substrate, the process including developing the substrate and removing the uncured portion in the laminate. It is possible to form a predetermined pattern by the method of forming the wiring pattern composed of the exposed regions.

Moreover, the photosensitive transfer sheet of this invention is a process of laminating | stacking on the board | substrate in the positional relationship where the 2nd photosensitive layer becomes a board | substrate side, and obtaining a laminated body (2) From the side of the 1st photosensitive layer of a laminated body , The light portion of the hole is irradiated with a relatively large amount of light irradiation to cure the first photosensitive layer and the second photosensitive layer together, and the wiring forming region to give a relatively small amount of light irradiation energy irradiation to cure the second photosensitive layer And (3) removing the support from the laminated body, and (4) developing the laminated body and removing the uncured portion in the laminate. On the substrate for forming a printed wiring board, a hole portion coated with a cured resin formed by curing the first photosensitive layer and a second photosensitive layer together, an area covered with a cured resin formed by curing the second photosensitive layer, and a substrate surface It is also possible to form a predetermined pattern by the method of forming the wiring pattern composed of the exposed regions.

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

As a light source of light irradiation in a process (2), when light irradiation is performed through a support body, the light source which permeate | transmits a support body and is mentioned above is used. As a light source, it is preferable to carry out by irradiation of a laser beam.

Then, in order to obtain a printed wiring board, the method of performing the process of etching or plating the board | substrate for printed wiring board formation in which the said wiring pattern was formed, for example, a well-known subtractive method or an additive method (semiadditive method, pull Additive method). It is preferable to use the subtractive method by etching for the purpose of forming a printed wiring board by industrially advantageous tenting of this invention. The cured resin remaining on the substrate for forming a printed wiring board after the treatment may be peeled off, and in the case of the semi-additive method, the copper thin film portion may be further etched after the peeling to form a desired printed wiring board. Moreover, a multilayer printed wiring board can also be manufactured like 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. 11 shows the case where the photosensitive transfer sheet shown in FIG. 1 or the photosensitive transfer sheet shown in FIG. 4 is used, but the barrier layer 13 is included even when the photosensitive transfer sheet shown in FIG. 1 or FIG. 3 is used. It is the same except not doing.

First, as shown to part (A) of FIG. 11, the printed wiring board formation board | substrate 21 which has the through-hole 22 and whose surface was covered with the metal plating layer 23 is prepared. As the printed wiring board forming substrate 21, a substrate in which a copper plating layer is formed on an insulating substrate such as a copper clad laminated substrate and a glass-epoxy or an interlayer insulating film is laminated on these substrates and a copper plating layer is formed (laminated substrate). Can be used.

Next, as shown to part (B) of FIG. 11, when the photosensitive transfer sheet 10 has a protective film, this protective film is peeled off, and the 2nd photosensitive layer 14 is a board | substrate for printed wiring board formation ( 21 is pressed to use the pressure roller 31 in contact with the surface (lamination step). As a result, a laminate in which the substrate 21 for forming a printed wiring board, 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 | stacking of the photosensitive transfer sheet can be performed at room temperature (15-30 degreeC) or heating (30-180 degreeC). In particular, it is preferable to carry out under 60-140 degreeC heating. It is preferable that the roll pressure of a crimping roll exists in the range of 1-10 kg / cm <2>. It is preferable to make a crimping speed into the speed of 1-3 m / min. Moreover, you may preheat the board | substrate 21 for printed wiring board formation. Moreover, you may laminate | stack under reduced pressure.

Instead of using the photosensitive transfer sheet, the second photosensitive resin composition solution, barrier layer solution, and first photosensitive resin composition solution for photosensitive transfer sheet manufacture are applied directly to the surface of the substrate for forming a printed wiring board in this order and dried. A laminate in which a substrate for forming a printed wiring board, a second photosensitive layer, a barrier layer, and a first photosensitive layer are laminated in this order can also be obtained.

Next, as shown to part (C) of FIG. 11, light is irradiated from the surface of the support body 11 side of a laminated body, and a photosensitive layer is hardened | cured. In addition, you may irradiate light after peeling a support body as needed (for example, when the light transmittance of a support body is inadequate). In the wiring pattern forming region of the printed wiring board forming substrate 21, light of the amount of light energy required to cure the second photosensitive layer 14 is irradiated onto a predetermined pattern to form a cured layer 16 for forming a wiring pattern. ) Is formed (wiring part exposure step). The opening of the through hole 22 of the substrate for forming a printed wiring board and the periphery thereof are irradiated with light having an amount of light energy required to cure the first photosensitive layer 12 and the second photosensitive layer 14, respectively. An area of the hardened layer 17 for protecting the metal layer is formed (hole exposure step). Although the wiring part exposure process and the hole part exposure process may be performed independently, it is more preferable to carry out in parallel. Exposure is performed by irradiating light through a photomask, or by irradiating a laser beam using a laser exposure apparatus. In particular, the method of using the latter laser exposure apparatus can be formed without using an expensive mask, and therefore, there is no problem in processing due to the mask, and therefore, it is suitable for production of small quantities of various kinds of products.

When irradiating light through a photomask, the amount of light energy which hardens only a 2nd photosensitive layer is irradiated through the area | region formation photomask of the hardening layer 16 for wiring pattern formation, and the hardening layer for protecting a metal layer of a through hole The method of performing exposure twice to irradiate the amount of light energy which hardens both the 2nd photosensitive layer and the 1st photosensitive layer through the photomask for region formation of (17) can also be used. Or collectively using a photomask prepared such that the light transmittance corresponding to the region of the cured layer 16 for forming the wiring pattern is low, and the light transmittance corresponding to the region of the cured layer 17 for protecting the through hole metal layer is high. Exposure can also be performed. On the other hand, when irradiating a laser beam using a laser exposure apparatus, it is preferable to perform scanning exposure, changing the light irradiation amount in each required area.

When the support is not yet peeled off, as shown in part (D) of FIG. 11, the support 11 is peeled from the laminate (support peeling step).

Next, as shown to (E) of FIG. 11, the uncured area | region of the 1st photosensitive layer 12, the barrier layer 13, and the 2nd photosensitive layer 14 on the printed wiring board formation board 21 is It melt | dissolves and removes with a suitable developing solution, the pattern of the hardening layer 16 for wiring pattern formation, and the hardening layer 17 for metal layer protection of a through hole is formed, and the metal plating layer 23 of the board | substrate surface is exposed (developing process). As a developing solution, you may use the developing solution corresponding to the photosensitive resin composition, such as alkaline aqueous solution, an aqueous developing solution, and an organic solvent. As a developing solution, a weak alkaline aqueous solution is preferable. Examples of the basic components of Alkali solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, potassium phosphate, sodium pyrophosphate, pyrophosphate Potassium, borax, etc. are mentioned. Moreover, it is preferable that pH of the weak alkaline aqueous solution used for image development is about 8-12, especially about 9-11. Specifically, 0.1-5 mass% sodium carbonate aqueous solution, potassium carbonate aqueous solution, etc. can be used. Moreover, although the temperature of a developing solution can be adjusted according to the developability of a photosensitive layer, generally 25 degreeC-40 degreeC is preferable. In addition, surfactants, antifoaming agents, organic bases (e.g., ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) and development are promoted in the developer. You may use together organic solvents (alcohols, ketones, esters, ethers, amides, lactones, etc.) in order to make it do. As the developing solution, an aqueous developing solution obtained by mixing water or an alkaline aqueous solution and an organic solvent may be used, or an organic solvent alone may be used.

In addition, after development, a treatment may be further performed to further accelerate the curing reaction of the hardened portion by post-heating treatment or post-exposure treatment. The development may be the above-described wet development method or may be performed by a dry development method.

Next, as shown to part (F) of FIG. 11, the exposed metal layer 23 on the surface of a board | substrate is melt | dissolved and removed by etching liquid (etching process). 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 formed in a predetermined shape without the etching liquid entering the through hole to corrode the metal plating in the through hole. Will remain. Thereby, the wiring pattern 24 is formed in the board 21 for forming a printed wiring board. When the metal layer 23 is formed of copper, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, a hydrogen peroxide etching solution, or the like can be used as the etching solution. Among these, a ferric chloride solution is especially preferable at the point of an etching factor.

Next, as shown to the (G) part of FIG. 11, in the strong alkali aqueous solution etc., the hardened layers 16 and 17 are used as the peeling piece 18, and it removes from the board | substrate for printed wiring board formation (hardening removal process). Examples of the base component of the strong alkaline aqueous solution include sodium hydroxide and potassium hydroxide. Moreover, it is preferable that pH of the strong alkaline aqueous solution used is about 12-14, Especially about 13-14. Specifically, 1-10 mass% sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, etc. can be used.

In addition, the printed wiring board may be a printed wiring board of a multilayer structure. The photosensitive transfer sheet of the present invention may be used not only for the above etching process but also for the plating process. As the plating method, for example, copper plating such as copper sulfate plating, copper pyrophosphate plating, solder plating such as high-slow solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, hard gold plating, soft Gold plating such as gold plating;

EXAMPLE

Synthesis Example 1 Synthesis of Polyurethane Resin

13.4 parts by mass of 2,2-bis (hydroxymethyl) propionic acid was dissolved in 57.6 parts by mass of N, N-dimethylacetamide. 25.0 mass parts of 4, 4- diphenylmethane diisocyanate and 0.1 mass part of dibutyltin dilaurylates were added to this, and it heated and stirred at 90 degreeC for 7 hours. Thereafter, 1-methoxy-2-propanol Polyurethane resin solution (solid content 35wt%) was obtained by adding 13.8 mass parts. The molecular weight was measured by gel permeation chromatography (GPC), and was 75000 by weight average molecular weight (based on polystyrene).

Example 1

The 1st photosensitive resin composition solution which consists of the following composition was apply | coated to the 20-micrometer-thick polyethylene terephthalate film, and it dried and formed the photosensitive layer (1st photosensitive layer) of 20 micrometers thickness.

[Composition of Solution of First Photosensitive Resin Composition]

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25 parts by mass of the polyurethane resin solution (solid content 35% by mass) synthesized in Synthesis Example 1

8 parts by mass of the following polymerizable compound (a)

0.5 parts by mass of p-toluenesulfonamide

0.04 parts by mass of 1,4-bis (N, N-diethylamino) benzophenone

1.0 parts by mass of benzophenone

0.5 parts by mass of 4-toluenesulfonamide

Malachite green oxalate 0.02 parts by mass

0.01 part by mass of 3-morpholinomethyl-1-phenyltriazole-2-thione

0.2 mass parts of leuco crystal violet

0.1 parts by mass of tribromomethylphenyl sulfone

Methyl ethyl ketone 30 parts by mass

───────────────────────────────────

Polymerizable Compound (a)

Next, the water-soluble polymer solution which consists of the following composition was apply | coated on the 1st photosensitive layer, and it dried and formed the barrier layer of 1.6 micrometer thickness.

Composition of Water-Soluble Polymer Solution

───────────────────────────────────

13 parts by mass of polyvinyl alcohol (PVA205: Clare KK)

6 parts by mass of polyvinylpyrrolidone (PVPK30: manufactured by GAF)

200 parts by mass of water

Methanol 180 parts by mass

───────────────────────────────────

Next, the 2nd photosensitive resin composition solution which consists of the following composition was apply | coated on the barrier layer, and it dried, and formed the 5 micrometers photosensitive layer (second photosensitive layer).

[Composition of Second Photosensitive Resin Composition Solution]

───────────────────────────────────

25 parts by mass of a polyurethane resin solution (solid content 35% by mass) synthesized in Synthesis Example 1

8 parts by mass of the polymerizable compound (a)

0.5 parts by mass of p-toluenesulfonamide

0.4 parts by mass of 1,4-bis (N, N-diethylamino) benzophenone

Benzophenone 3.0 parts by mass

Malachite green oxalate 0.02 parts by mass

0.01 part by mass of 3-morpholinomethyl-1-phenyltriazole-2-thione

0.2 mass parts of leuco crystal violet

0.1 parts by mass of tribromomethylphenyl sulfone

Methyl ethyl ketone 30 parts by mass

───────────────────────────────────

Finally, a 20-micrometer-thick polyethylene film was laminated on the second photosensitive layer to obtain a photosensitive transfer sheet. Neither layer had a layer thickness nonuniformity within ± 5%. The sensitivity of the photosensitive transfer sheet thus obtained was measured by the method described below. The shortest developing time was 20 seconds, and the amount of light energy A required to cure the second photosensitive layer was 4 mJ / cm ² . The amount of light energy B required for curing is 40 mJ / cm ² , and the amount of light energy C required until the curing of the first photosensitive layer starts is 14 mJ / cm ² (a ratio C / A between the amount of light energy C and the amount of light energy A). Was 3.5 and the ratio A / B of the amount of light energy A and the amount of light energy B was 0.1). In addition, when the photosensitivity of the first photosensitive layer was 1, the photosensitivity of the second photosensitive layer was 10.

Example 2

A photosensitive transfer sheet was produced in the same manner as in Example 1 except that the thickness of the first photosensitive layer was 10 μm. Neither layer had a layer thickness nonuniformity within ± 5%. The sensitivity of the photosensitive transfer sheet thus obtained was measured by the method described below. The shortest developing time was 15 seconds, and the amount of light energy A required to cure the second photosensitive layer was 4 mJ / cm ² . The amount of light energy B required for curing is 30 mJ / cm ² , and the amount of light energy C required until the curing of the first photosensitive layer starts is 10 mJ / cm ² (the ratio C / A of the amount of light energy C and the amount of light energy A). The ratio A / B between 2.5 and the amount of light energy A and the amount of light energy B was 0.13). In addition, when the light sensitivity of the first photosensitive layer was 1, the light sensitivity of the second photosensitive layer was 7.5.

Example 3

25 mass parts of polyurethane resin solutions of the 2nd photosensitive layer of Example 1 are methyl methacrylate / styrene / benzyl methacrylate / methacrylic acid copolymer solution (copolymer composition (mass ratio): 8/30/37/25 , Mass average molecular weight: 60000, Tg: 105 ° C, 35.0 mass% of solid content), 25 parts by mass, 8.0 parts by mass of the polymerizable compound (a), 6.5 parts by mass of dodeca polypropylene glycol diacrylate, tetraethylene glycol dimetha A photosensitive transfer sheet was produced in the same manner as in Example 1, except that the acrylate was changed to 1.5 parts by mass, and the film thickness nonuniformity of either layer was within ± 5%. According to the measurement, the shortest developing time was 25 seconds, and the amount of light energy A required to cure the second photosensitive layer was 4 mJ / cm ² , and the amount of light energy B required to cure the first photosensitive layer was 40 mJ. and / cm ^2, 1, light energy required for the curing of the photosensitive layer is started the amount of C is of 14mJ / cm ² (light energy amount C and the ratio C / A of the light energy amount A is 3.5, the light energy amount A and the light energy amount B ratio A / B was 0.1) In the case where the light sensitivity of the first photosensitive layer was 1, the light sensitivity of the second photosensitive layer was 10.

Example 4

25 mass parts of polyurethane resin solutions of the 1st photosensitive layer of Example 1 are methyl methacrylate / styrene / benzyl methacrylate / methacrylic acid copolymer solution (copolymer composition (mass ratio): 8/30/37/25 The photosensitive transfer sheet | seat was created by the method similar to Example 1 except having changed to 25 mass parts of mass mean molecular weights: 60000, Tg: 105 degreeC, and 35.0 mass% of solid content. The sensitivity of the photosensitive transfer sheet thus obtained was measured by the method described below. The shortest developing time was 25 seconds, and the amount of light energy A required to cure the second photosensitive layer was 4 mJ / cm ² , The amount of light energy B required to cure the first photosensitive layer is 40 mJ / cm ² , and the amount of light energy C required until the curing of the first photosensitive layer starts is 14 mJ / cm ² (light energy amount C and light energy amount A The ratio C / A is 3.5, and the ratio A / B of the amount of light energy A and the amount of light energy B is 0.1). Moreover, when the photosensitivity of the first photosensitive layer was made to 1, the photosensitivity of the second photosensitive layer was 10.

Example 5

A photosensitive transfer sheet of Example 5 was prepared in the same manner as in Example 1 except that no barrier layer was added. Neither layer had a film thickness nonuniformity within ± 5%. The sensitivity of the photosensitive transfer sheet thus obtained was measured by the method described below. The shortest developing time was 20 seconds, and the amount of light energy A required to cure the second photosensitive layer was 4 mJ / cm ² , and the first photosensitive layer was used. The amount of light energy B required to cure is 40 mJ / cm ² , and the amount of light energy C required until the curing of the first photosensitive layer starts is 14 mJ / cm ² (the ratio C / of light energy amount C and light energy amount A / A was 3.5 and ratio A / B of the amount of light energy A and the amount of light energy B was 0.1). In addition, when the light sensitivity of the first photosensitive layer was 1, the light sensitivity of the second photosensitive layer was 10.

Example 6

25 mass parts of 1st photosensitive layer polyurethane resins of Example 1 are methyl methacrylate / styrene / benzyl methacrylate / methacrylic acid copolymer solution (copolymer composition (mass ratio): 8/30/37/25, mass) Average molecular weight: 60000, Tg: 105 DEG C, 35.0 mass% of solid content) 15 mass parts, 8.0 mass parts of polymeric compounds (a), 6.5 mass parts of dodeca polypropylene glycol diacrylates, and tetraethylene glycol dimethacrylate It carries out except changing into 1.5 mass parts, and changing 8.0 mass parts of polymeric compounds (a) of a 2nd photosensitive layer to 6.5 mass parts of dodeca polypropylene glycol diacrylates, and 1.5 mass parts of tetraethylene glycol dimethacrylates. A photosensitive transfer sheet was prepared in the same manner as in Example 1. The film thickness nonuniformity of both layers was within ± 5% .The sensitivity of the photosensitive transfer sheet thus obtained was measured by the method described below, resulting in the shortest developing time. 25 seconds, the light energy amount A required for curing the second photosensitive layer is 4mJ / cm ^2, the first optical energy amount B required in order to cure the photosensitive layer is 40mJ / cm ^2, curing of the first photosensitive layer Until the start, the required amount of light energy C was 14 mJ / cm ² (the ratio C / A of light energy amount C and light energy amount A was 3.5 and the ratio A / B of light energy amount A and light energy amount B was 0.1). In addition, when the photosensitivity of the first photosensitive layer was 1, the photosensitivity of the second photosensitive layer was 10.

Comparative Example 1

The photosensitive transfer sheet | seat was produced by the method similar to Example 1 except having changed the film thickness of the 1st photosensitive layer in Example 6, and not applying a barrier layer and a 2nd photosensitive layer. The sensitivity of the photosensitive transfer sheet thus obtained was measured by the method described below. The shortest developing time was 15 seconds and the amount of light energy required to cure the photosensitive layer was 40 mJ / cm ² .

[Measuring method of sensitivity]

(1) Measurement method of shortest developing time

The photosensitive transfer sheet was laminated by polishing the surface of the photosensitive transfer sheet to remove the protective film of the photosensitive transfer sheet on the surface of the copper clad laminate (no through hole), so that the second photosensitive layer of the photosensitive transfer sheet was in contact with the substrate (MODEL8B-720). -PH, manufactured by Taisei Laminator Co., Ltd.), to form 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. do. The crimping conditions were crimping roll temperature 105 degreeC, crimping roll pressure 3 kg / cm <^2> , and crimping | compression-rate 1m / min. A polyethylene terephthalate film is peeled off from a laminated body, and 30 mass% 1 mass% sodium carbonate aqueous solution is sprayed at 0.15 Mpa on the whole surface of the photosensitive layer on a copper clad laminated board. The time required from the start of the spray of the aqueous solution of sodium carbonate to the photosensitive layer on the copper clad laminate is dissolved and removed, and this is defined as the shortest developing time.

(2) measurement of sensitivity

The photosensitive transfer sheet is laminated on the substrate in the same manner as the shortest developing time. The photosensitive layer of the photosensitive transfer sheet, polyethylene terephthalate and the film side using an exposure device having a laser light source of 405nm, a second ^one-half times the distance to another amount of light energy to 100mJ / cm ² light from 0.1mJ / cm ² It irradiates and hardens a photosensitive layer. After standing at room temperature for 10 minutes, the polyethylene terephthalate film is peeled off from the laminate. 30 mass of 1 mass% sodium carbonate aqueous solution is sprayed on the whole surface of the resin composition layer on a copper clad laminated board for 2 times of the shortest developing time calculated | required in said (1) by spray pressure 0.15 MPa, and the uncured resin composition is melt | dissolved. It removes and measures the thickness of the remaining hardened layer. Subsequently, the relationship between the irradiation amount of light and the thickness of the cured layer is plotted to obtain a sensitivity curve. From the sensitivity curve thus obtained, the amount of light energy (light energy amount A) and the cured layer when the thickness of the cured layer becomes 5 μm is obtained. The amount of light energy (light energy amount B) and the thickness of the cured layer when the thickness of 26.6 μm (16.6 μm in Example 2, 25 μm in Example 5, 25 μm in Comparative Example 1) became 5 μm The amount of light energy (light energy amount C) when exceeding is read.

[Measurement method of resolution]

On the same conditions as the evaluation method of shortest developing time of said (1), the laminated body by which the copper clad laminated board, the 2nd photosensitive layer, the 1st photosensitive layer, and the polyethylene terephthalate film were laminated | stacked in this order was created, and room temperature (23 degreeC) , 55% RH) for 10 minutes. From the polyethylene terephthalate film of the obtained laminated body, the width | variety of the exposure part and the unexposed part was exposed through the line pattern of the ratio of 1: 1. Exposure was performed with the high pressure mercury lamp exposure machine (oak HMW-532D), and exposure amount was made into the said optical energy amount B. Subsequently, after leaving still at room temperature for 10 minutes, a polyethylene terephthalate film is peeled off from a laminated body. A 30 mass% 1 mass% sodium carbonate aqueous solution is sprayed on the whole surface of the resin composition layer on a copper clad laminated board for 2 times of the shortest development time calculated | required above by spray pressure of 0.15 Mpa, and the uncured resin composition is dissolved and removed. The surface of the copper clad laminate with a cured resin pattern thus obtained was observed with an optical microscope, and the minimum line width without abnormalities such as clogging and wrinkles was measured on the line with the cured resin pattern, which is referred to as resolution. The smaller the value, the better the resolution.

[Tent film breakage rate]

A copper plating layer was formed on the inner wall, and the second photosensitive layer of the photosensitive transfer sheet on which the protective film was peeled was laminated and laminated on a copper clad laminate whose surface was polished, washed, and dried. By the method, the laminated body in which the copper clad laminated board, the 2nd photosensitive layer, the barrier layer, the 1st photosensitive layer, and the polyethylene terephthalate film were laminated | stacked in this order was created, and it left still for 10 minutes at room temperature (23 degreeC, 55% RH). From the polyethylene terephthalate film of the obtained laminated body, the whole photosensitive layer was exposed by the light quantity of the said optical energy amount B using the high pressure mercury lamp exposure machine. Subsequently, the polyethylene terephthalate film was peeled off from the laminated body, and 30 degreeC 1 mass% sodium carbonate aqueous solution was sprayed for 1.5 times the time of the shortest development time calculated | required above by spray pressure of 0.2 MPa. The ratio of the number of holes in which the tent film was broken with respect to the total number of holes in the copper clad laminate was taken as the tent film failure rate. The lower the tent break rate, the better.

Table 1 shows the results of evaluating the resolution and the tent film breakage rate for the photosensitive transfer sheet.

First photosensitive layer                                              Barrier layer Second photosensitive layer                                              resolution Tent Breakage Rate bookbinder Thickness (㎛) bookbinder Thickness (㎛) Example 1 Polyurethane resin 20 has exist Polyurethane resin 5 20㎛ or less 3% less than Example 2 Polyurethane resin 10 has exist Polyurethane resin 5 20㎛ or less 3% less than Example 3 Polyurethane resin 20 has exist Vinyl copolymer 5 20㎛ or less 3% less than Example 4 Vinyl copolymer 20 has exist Polyurethane resin 5 20㎛ or less 3% less than Example 5 Polyurethane resin 20 none Polyurethane resin 5 20㎛ or less 3% less than Example 6 Vinyl copolymer 20 has exist Polyurethane resin 5 20㎛ or less 3% less than Comparative Example 1 Vinyl copolymer 25 - - Exceeds 30 μm 20% less than

As shown in Table 1, the photosensitive transfer sheet of the multilayer structure which introduce | transduced the polyurethane resin into the 1st photosensitive layer or the 2nd photosensitive layer is compatible with both tentability and resolution. In particular, when a polyurethane resin is introduced into both layers of the first photosensitive layer and the second photosensitive layer, the tentability is good even if the film thickness is reduced to 15 mu m (excluding the barrier layer).

The photosensitive transfer sheet and the photosensitive laminated body of this invention can form the hardened layer which differs in thickness by changing the irradiation amount (it can be called exposure amount) of the light. Therefore, when image formation is performed using the photosensitive transfer sheet or the photosensitive laminate of the present invention, a cured layer having an arbitrary thickness can be formed for each desired region (a three-dimensional image can be formed), and the desired region is desired. There are numerous advantages, such as the amount of light transmitted per each change (the density of the image can be changed), the formation of a cured layer showing the desired film strength for each desired area, and the like. For example, in the region where the film strength of the cured layer is to be strengthened, in the region where the thickness of the cured layer is to be thick and in the region where the resolution is to be increased, the pattern formation that makes the thickness of the cured layer thin is also possible.

In particular, as a result of the research of the present inventors, it was found that the use of the polyurethane resin in the binder of the first photosensitive layer and / or the second photosensitive layer makes it possible to form a hardened layer having a high strength. In other words, it has been found that it is possible to form a high-strength hardened layer (tent film) even if the thickness of the photosensitive layer is reduced for high resolution.

Therefore, when the photosensitive transfer sheet and the photosensitive laminated body of this invention are used for manufacture of a printed wiring board, especially the manufacture of the printed wiring board which has hole parts, such as a through hole and a via hole, it is relatively thin in a wiring pattern formation area, A high resolution cured layer can be formed, and a through layer or via hole can be formed with a relatively thick and high strength cured layer. For this reason, by using this invention, a high-resolution printed wiring board can be manufactured by the industrially advantageous tenting method.

Claims (41)

It consists of the 1st photosensitive layer which consists of a photosensitive resin composition containing a binder, a polymeric compound, and a photoinitiator on a support body, and the photosensitive resin composition containing a binder, a polymeric compound, and a photoinitiator, Than the photosensitivity of a 1st photosensitive layer A photosensitive transfer sheet, wherein a second photosensitive layer having a relatively high light sensitivity is laminated in this order, and at least one binder of the first photosensitive layer and the second photosensitive layer is a polyurethane resin. The photosensitive transfer sheet according to claim 1, wherein the polyurethane resin has a carboxyl group. The photosensitive transfer sheet according to claim 1 or 2, wherein the binder of the first photosensitive layer is a polyurethane resin. The photosensitive transfer sheet according to claim 1 or 2, wherein the binder of the second photosensitive layer is a polyurethane resin. The photosensitive transfer sheet according to claim 1 or 2, wherein the binders of the first photosensitive layer and the second photosensitive layer are both polyurethane resins. The photosensitive transfer sheet according to claim 1 or 2, wherein a barrier layer is disposed between the first photosensitive layer and the second photosensitive layer. 7. The photosensitive transfer sheet according to claim 6, wherein the barrier layer contains, as a main component, a resin having affinity for water or lower alcohols having 1 to 4 carbon atoms. The photosensitive transfer sheet according to claim 6, wherein the barrier layer contains a soluble resin as a main component of water or a lower alcohol having 1 to 4 carbon atoms. 7. The photosensitive transfer sheet according to claim 6, wherein the barrier layer has a thickness in the range of 0.1 to 5 mu m. The photosensitive transfer sheet according to claim 1 or 2, wherein 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. The ratio represented by A / B of the amount of light energy A required for curing the second photosensitive layer and the amount of light energy B required for curing the first photosensitive layer is 0.005 to 0.5. Photosensitive transfer sheet, characterized in that in the range. The ratio represented by C / A of the amount of light energy A necessary for curing the second photosensitive layer and the amount of light energy C required until the curing of the first photosensitive layer is started, wherein the ratio is from 1 to 2. The photosensitive transfer sheet characterized by being in the range of 10. The photosensitive transfer sheet according to claim 1 or 2, wherein each of the first photosensitive layer and the second photosensitive layer contains a sensitizer. The photosensitive transfer sheet according to claim 13, wherein the amount of the sensitizer contained in the second photosensitive layer is greater than the amount of the sensitizer contained in the first photosensitive layer. The photosensitive transfer sheet according to claim 1 or 2, wherein the amount of the photopolymerization initiator contained in the second photosensitive layer is greater than the amount of the photopolymerization initiator contained in the first photosensitive layer. The photosensitive transfer sheet according to claim 1 or 2, wherein the amount of the polymerizable compound contained in the second photosensitive layer is greater than the amount of the polymerizable compound contained in the first photosensitive layer. The photosensitive transfer sheet according to claim 1 or 2, wherein the first photosensitive layer has a thickness in the range of 1 to 100 µm and the thickness thereof is larger than the thickness of the second photosensitive layer. The photosensitive transfer sheet according to claim 1 or 2, wherein the second photosensitive layer has a thickness in the range of 0.1 to 15 mu m. The photosensitive transfer sheet according to claim 1 or 2, wherein the support is a synthetic resin agent and is transparent. The photosensitive transfer sheet according to claim 1 or 2, wherein the support is a long support. The photosensitive transfer sheet according to claim 1 or 2, wherein a protective film is arranged on the second photosensitive layer. The photosensitive transfer sheet according to claim 1 or 2, which is a long body and wound in a roll shape. The photosensitive transfer sheet according to claim 1 or 2, which is for manufacturing a printed wiring board. It consists of the 2nd photosensitive layer which consists of a photosensitive resin composition containing a binder, a polymeric compound, and a photoinitiator on a base material, and the photosensitive resin composition containing a binder, a polymeric compound, and a photoinitiator, Than the photosensitivity of a 2nd photosensitive layer A first photosensitive layer having a relatively low light sensitivity is laminated in this order, and at least one binder of the first photosensitive layer and the second photosensitive layer is a polyurethane resin. 25. The photosensitive laminate according to claim 24, wherein a barrier layer is disposed between the first photosensitive layer and the second photosensitive layer. The photosensitive laminate according to claim 25, wherein the barrier layer contains, as a main component, a resin showing affinity for water or lower alcohols having 1 to 4 carbon atoms. The photosensitive laminate according to claim 25 or 26, wherein the barrier layer contains a soluble resin as a main component of water or a lower alcohol having 1 to 4 carbon atoms. 27. The photosensitive laminate according to any one of claims 24 to 26, wherein the substrate is a substrate for forming a printed wiring board. 27. The photosensitive laminate according to any one of claims 24 to 26, wherein a support is laminated on the first photosensitive layer. A method of forming an image pattern composed of a region having a cured resin layer formed by curing the first photosensitive layer and a second photosensitive layer together on a substrate and a region having no cured resin layer present, (1) Process of laminating | stacking the photosensitive transfer sheet of Claim 1 on a board | substrate in the positional relationship whose 2nd photosensitive layer becomes a board | substrate side, and obtaining a laminated body; (2) irradiating a predetermined image pattern from the side of the first photosensitive layer of the laminated body, and curing the first photosensitive layer and the second photosensitive layer of the region subjected to the light irradiation together; (3) removing the support from the laminate; And, (4) A method for forming an image pattern comprising developing a laminate and removing uncured portions in the laminate. A method of forming an image pattern composed of a region having a cured resin layer formed by curing the first photosensitive layer and a second photosensitive layer together on a substrate and a region having no cured resin layer present, A step of laminating the photosensitive transfer sheet according to claim 1 on a substrate in a positional relationship in which the second photosensitive layer is the substrate side to obtain a laminate; Removing the support from the laminate; Irradiating a predetermined image pattern from the side of the first photosensitive layer of the laminate, and curing the first photosensitive layer and the second photosensitive layer of the region subjected to the light irradiation together; And, Developing a laminate and removing an uncured portion in the laminate. 32. The image pattern forming method according to claim 30 or 31, wherein light irradiation is performed by laser light irradiation. It consists of the area | region in which the resin layer formed by hardening | curing together the 1st photosensitive layer and the 2nd photosensitive layer exists on the board | substrate, the area | region in which the resin layer formed by hardening of the 2nd photosensitive layer exists, and the area | region in which the cured resin layer does not exist. As a method of forming an image pattern, (1) Process of laminating | stacking the photosensitive transfer sheet of Claim 1 on a board | substrate in the positional relationship whose 2nd photosensitive layer becomes a board | substrate side, and obtaining a laminated body; (2) From the side of the first photosensitive layer of the laminate, light is irradiated with an image pattern that defines a region for irradiating light of at least two levels of irradiation energy amounts different from each other, and light irradiation with a relatively large amount of light irradiation energy is applied. Curing the first photosensitive layer and the second photosensitive layer of the received region together, and curing the second photosensitive layer of the region subjected to light irradiation with a relatively small amount of light irradiation energy; (3) removing the support from the laminate; And, (4) A method for forming an image pattern comprising developing a laminate and removing uncured portions in the laminate. It consists of the area | region in which the resin layer formed by hardening | curing together the 1st photosensitive layer and the 2nd photosensitive layer exists on the board | substrate, the area | region in which the resin layer formed by hardening of the 2nd photosensitive layer exists, and the area | region in which the cured resin layer does not exist. As a method of forming an image pattern, Laminating | stacking the photosensitive transfer sheet of Claim 1 on a board | substrate in the positional relationship whose 2nd photosensitive layer becomes a board | substrate side, and obtaining a laminated body; Removing the support from the laminate; From the side of the first photosensitive layer of the laminate, the light is irradiated with an image pattern that defines a region for irradiating light having an amount of irradiation energy of at least two levels which are different from each other, and the region of the region subjected to light irradiation with a relatively large amount of irradiation energy Curing the first photosensitive layer and the second photosensitive layer together, and curing the second photosensitive layer in a region subjected to light irradiation with a relatively small amount of light irradiation energy; And, Developing a laminate and removing an uncured portion in the laminate. 35. An image pattern forming method according to claim 33 or 34, wherein light irradiation is performed by laser light irradiation. A method of forming a wiring pattern composed of a region covered with a cured resin layer formed by curing a first photosensitive layer and a second photosensitive layer together on a printed wiring board forming substrate and a region where the surface of the substrate is exposed, (1) Process of laminating | stacking the photosensitive transfer sheet of Claim 1 on a board | substrate in the positional relationship whose 2nd photosensitive layer becomes a board | substrate side, and obtaining a laminated body; (2) performing light irradiation of a predetermined wiring pattern from the side of the first photosensitive layer of the laminate, and curing the first photosensitive layer and the second photosensitive layer of the region subjected to the light irradiation together; (3) removing the support from the laminate; And, (4) A method of forming a wiring pattern, comprising the steps of developing a laminate and removing uncured portions in the laminate. A method of forming a wiring pattern comprising a region covered with a cured resin layer formed by curing a first photosensitive layer and a second photosensitive layer together on a printed wiring board forming substrate and a region where the surface of the substrate is exposed, Laminating | stacking the photosensitive transfer sheet of Claim 1 on a board | substrate in the positional relationship whose 2nd photosensitive layer becomes a board | substrate side, and obtaining a laminated body; Removing the support from the laminate; Irradiating a predetermined wiring pattern from the side of the first photosensitive layer of the laminate, and curing the first photosensitive layer and the second photosensitive layer in the region subjected to the light irradiation together; And, Developing the laminate and removing the uncured portion in the laminate. 38. The method of forming a wiring pattern according to claim 36 or 37, wherein light irradiation is performed by laser light irradiation. A hole portion coated with a cured resin layer formed by curing the first photosensitive layer and a second photosensitive layer together on a substrate for forming a printed wiring board having a hole portion, a region covered with a cured resin layer formed by curing the second photosensitive layer, and A method of forming a wiring pattern composed of an area where a substrate surface is exposed, (1) Process of laminating | stacking the photosensitive transfer sheet of Claim 1 on a board | substrate in the positional relationship whose 2nd photosensitive layer becomes a board | substrate side, and obtaining a laminated body; (2) From the side of the first photosensitive layer of the laminate, the hole portion is given light irradiation with a relatively large amount of light irradiation energy to cure the first photosensitive layer and the second photosensitive layer together, and to the wiring formation region, the light irradiation Performing light irradiation of an image pattern which gives light irradiation with a relatively small amount of energy to cure the second photosensitive layer; (3) removing the support from the laminate; And, (4) A method of forming a wiring pattern, comprising the steps of developing a laminate and removing uncured portions in the laminate. A hole portion coated with a cured resin layer formed by curing the first photosensitive layer and a second photosensitive layer on a substrate for forming a printed wiring board having a hole portion, a region covered with a cured resin layer formed by curing the second photosensitive layer, and In the method for forming a wiring pattern composed of a region where the substrate surface is exposed, Laminating | stacking the photosensitive transfer sheet of Claim 1 on a board | substrate in the positional relationship whose 2nd photosensitive layer becomes a board | substrate side, and obtaining a laminated body; Removing the support from the laminate; From the side of the first photosensitive layer of the laminate, the hole is irradiated with a relatively large amount of light irradiation energy to cure the first photosensitive layer and the second photosensitive layer together, and the amount of light irradiation energy is relative to the wiring formation region. Performing light irradiation of an image pattern to give a small light irradiation to cure the second photosensitive layer; And, And developing the laminate and removing the uncured portion in the laminate. The wiring pattern forming method according to claim 39 or 40, wherein light irradiation is performed by laser light irradiation.

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