JP2005331695A - Photosensitive transfer sheet, photosensitive laminate, image pattern forming method, and wiring pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive transfer sheet and a photosensitive laminate capable of easily forming desired patterns having mutually different thicknesses within an image. <P>SOLUTION: The photosensitive transfer sheet is obtained by sequentially stacking on a support a first photosensitive layer comprising a photosensitive resin composition containing a binder, a polymerizable compound and a photoinitiator and a second photosensitive layer comprising a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator and exhibiting a relatively higher photosensitivity than the first photosensitive layer. The photosensitive laminate includes the above first photosensitive layer and second photosensitive layer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

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

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

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

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

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

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

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

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

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

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

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

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

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

  The present invention provides a first photosensitive layer comprising a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator on a support having a light transmittance of 80% or more measured at a wavelength of 405 nm, and a binder , A photosensitive compound comprising a photosensitive resin composition containing a polymerizable compound and a photopolymerization initiator, and a second photosensitive layer having a higher photosensitivity than the photosensitivity of the first photosensitive layer is laminated in this order. On the transfer sheet. The support preferably has a haze of 11% or less measured at a wavelength of 405 nm.

  The present invention also provides a first photosensitive layer comprising a photosensitive resin composition comprising a binder, a polymerizable compound, and a photopolymerization initiator on a support having a light transmittance of 80% or more measured at a wavelength of 355 nm, and A photosensitive material comprising a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator, wherein a second photosensitive layer having a higher photosensitivity than the first photosensitive layer is laminated in this order. There is also a transfer sheet. The support preferably has a haze of 11% or less measured at a wavelength of 355 nm.

In this specification, the light transmittance at each wavelength of the support means the total light transmittance at each wavelength. The haze at each wavelength of the support is a value defined by the following formula from the values of light transmittance (total light transmittance) and parallel light transmittance at each wavelength.
Haze (%) = [light transmittance (total light transmittance) −parallel light transmittance] / light transmittance × 100

Preferred embodiments of the photosensitive transfer sheet of the present 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 a resin having an affinity for water or a lower alcohol having 1 to 4 carbon atoms as a main component.
(3) The barrier layer contains, as a main component, a resin that is 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 μm.
(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 expressed by A / B between the amount of light energy A necessary for curing the second photosensitive layer and the amount of light energy B necessary for curing the first photosensitive layer is 0.005. It is in the range of 0.5.
(7) The ratio represented by C / A between the amount of light energy A required to cure the second photosensitive layer and the amount of light energy C required until the first photosensitive layer begins to cure is 1 to 10 It is in the range.
(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 larger than the amount of the sensitizer contained in the first photosensitive layer.
(10) The amount of the photopolymerization initiator contained in the second photosensitive layer is larger than the amount of the photopolymerization initiator contained in the first photosensitive layer.

(11) The amount of the polymerizable compound contained in the second photosensitive layer is larger than the amount of the polymerizable compound contained in the first photosensitive layer.
(12) The first photosensitive layer has a thickness in the range of 1 to 100 μm, and the thickness is larger than the thickness of the second photosensitive layer.
(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.
(15) The synthetic resin forming the support is polyethylene terephthalate, polyethylene naphthalate, polyethylene, cellulose triacetate, cellulose diacetate, cellulose, polyacrylate ester, polymethacrylate ester, polyvinyl chloride, polyamide, polyimide, poly It is selected from the group consisting of vinyl acetate, polytetrafluoroethylene, polytrifluoroethylene and copolymers thereof.
(16) The support is a long support.
(17) A protective film is disposed on the second photosensitive layer.
(18) It is a long body and is wound in a roll shape.
(19) For printed wiring board manufacture.

  The present invention also provides a second photosensitive layer comprising a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator on a substrate, and a photosensitivity containing the binder, the polymerizable compound, and the photopolymerization initiator. A first photosensitive layer made of a resin composition and having a light sensitivity relatively lower than that of the second photosensitive layer, and a support having a light transmittance of 80% or more measured at a wavelength of 405 nm are laminated in this order. There is also a photosensitive laminate. The support preferably has a haze of 11% or less measured at a wavelength of 405 nm.

  The present invention further includes a second photosensitive layer comprising a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator on a substrate, and a photosensitivity containing the binder, the polymerizable compound, and the photopolymerization initiator. A first photosensitive layer comprising a resin composition and exhibiting a light sensitivity relatively lower than that of the second photosensitive layer, and a support having a light transmittance of 80% or more measured at a wavelength of 355 nm are laminated in this order. There is also a photosensitive laminate. The support preferably has a haze of 11% or less measured at a wavelength of 355 nm.

Preferred embodiments of the photosensitive laminate of the present 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 a resin having an affinity for water or a lower alcohol having 1 to 4 carbon atoms as a main component.
(3) The barrier layer contains, as a main component, a resin that is 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 μm.
(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 expressed by A / B between the amount of light energy A necessary for curing the second photosensitive layer and the amount of light energy B necessary for curing the first photosensitive layer is 0.005. It is in the range of 0.5.
(7) The ratio represented by C / A between the amount of light energy A required to cure the second photosensitive layer and the amount of light energy C required until the first photosensitive layer begins to cure is 1 to 10 It is in the range.
(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 larger than the amount of the sensitizer contained in the first photosensitive layer.
(10) The amount of the photopolymerization initiator contained in the second photosensitive layer is larger than the amount of the photopolymerization initiator contained in the first photosensitive layer.

(11) The amount of the polymerizable compound contained in the second photosensitive layer is larger than the amount of the polymerizable compound contained in the first photosensitive layer.
(12) The first photosensitive layer has a thickness in the range of 1 to 100 μm, and the thickness is larger than the thickness of the second photosensitive layer.
(13) The second photosensitive layer has a thickness in the range of 0.1 to 15 μm.
(14) The substrate is a printed wiring board forming substrate.
(16) For printed wiring board manufacture.

The present invention also includes the following steps: a region where a cured resin layer formed by curing both the first photosensitive layer and the second photosensitive layer on the substrate and a region where there is no cured resin layer; There is also a method of forming an image pattern composed of:
(1) A step of laminating the photosensitive transfer sheet of the present invention on a substrate in a positional relationship such that the second photosensitive layer is on the substrate side;
(2) A step of performing light irradiation of a predetermined image pattern from the side of the first photosensitive layer of the laminate and curing both the first photosensitive layer and the second photosensitive layer in the region irradiated with the light;
(3) removing the support from the laminate; and
(4) The process of developing a laminated body and removing the unhardened part in a laminated body.

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

  In the image forming method of the present invention, the light irradiation in the step (2) is preferably performed by laser light irradiation.

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

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

  In the wiring pattern forming method of the present invention, the light irradiation in the step (2) is preferably performed by laser light irradiation.

  In the photosensitive transfer sheet and the photosensitive laminate of the present invention, a cured layer having a different thickness can be formed in an arbitrary region by changing the light irradiation amount (in other words, the exposure amount). Accordingly, when an image is formed using the photosensitive transfer sheet or photosensitive laminate of the present invention, a cured layer having an arbitrary thickness can be formed in each desired region (forming a three-dimensional image). The amount of transmitted light can be changed for each desired region (the density of the image can be changed), a cured layer showing a desired film strength can be formed for each desired region, etc. There are a number of advantages. For example, it is possible to form a pattern in which the thickness of the cured layer can be increased in a region where the film strength of the cured layer is desired to be increased, and in the region where the resolution is desired to be increased, the thickness of the cured layer is decreased. In particular, in the photosensitive transfer sheet and the photosensitive laminate of the present invention, the light transmittance of the support measured at a wavelength of 405 nm is 90% or more, or the light transmittance of the support measured at a wavelength of 355 nm is 87% or more. Therefore, it is advantageous when image formation is performed by irradiation with laser light while the support is laminated.

  Therefore, when the photosensitive transfer sheet and the photosensitive laminate of the present invention are used for manufacturing a printed wiring board, particularly a printed wiring board having a hole portion such as a through hole or a via hole, Accordingly, a high-resolution hardened layer having a relatively small thickness can be formed, and a high-strength hardened layer having a relatively thick thickness can be formed in the through hole or via hole. Therefore, by using the present invention, a high-resolution printed wiring board can be manufactured by an industrially advantageous tenting method.

[Basic configuration]
As an example of the photosensitive transfer sheet of the present invention, schematic sectional views of a constitution having two photosensitive layers are shown in FIGS.

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

  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 in which this barrier layer is disposed is preferable. FIG. 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 a protective film 15 is further laminated on the photosensitive transfer sheets of FIGS. 1 and 2, respectively.

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

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

  The layer structure of the photosensitive transfer sheet of the present invention is not limited to the layer structure illustrated in FIGS. 1 to 4 described above, and may have layers other than the layers illustrated in FIGS. 1 to 4. . For example, between the support 11 and the first photosensitive layer 12, or between the protective film 15 and the second photosensitive layer 14, a layer for adjusting the peelability and adhesion between the support and the substrate, an antihalation layer, Alternatively, a barrier layer or the like may be provided. In this case, the barrier layer has a role of preventing or suppressing migration of substances contained in the photosensitive layer, the support, or the protective film, and preventing or suppressing external influences such as oxygen and humidity.

  Next, the relationship between the light irradiation amount and the photosensitive layer curing amount in the photosensitive transfer sheet and photosensitive laminate of the present invention will be described with reference to FIG. In FIG. 5, for example, the photosensitive transfer sheet shown in FIG. 1 or the photosensitive transfer sheet from which the protective film was peeled off from the photosensitive transfer sheet shown in FIG. 3 was transferred onto a substrate to form a laminate. In the case of irradiating the photosensitive layer with light from the opposite side of the substrate from the side opposite to the substrate through the support, if necessary, or peeling the support as necessary 2 is a graph (sensitivity curve) showing the relationship between the amount of light irradiation, the irradiation (exposure), and the thickness of the cured layer generated by the subsequent development processing. In FIG. 5, the horizontal axis represents the amount of light irradiation, and the vertical axis represents the thickness of the cured layer obtained after being cured by light irradiation and developed. D on the vertical axis is the thickness of the cured layer formed from the second photosensitive layer, and E is 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. Represents the thickness.

  As shown in FIG. 5, in the photosensitive transfer sheet of the present invention, the light irradiated from the support side, in the case of having the support, proceeds in the order of the support, the first photosensitive layer, and the second photosensitive layer. The curing of the second photosensitive layer starts with a small amount of light energy prior to the first photosensitive layer. Then, after the entire second photosensitive layer is cured, when the amount of light energy is increased, curing of the first photosensitive layer starts, and when the amount of light energy is further increased, the entire first photosensitive layer is cured.

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

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

  Even when a barrier layer is provided between the first photosensitive layer and the second photosensitive layer as in the photosensitive transfer sheet shown in FIGS. 2 and 4, the light irradiation amount and the thickness of the cured layer are the same as those in FIG. This relationship is obtained. However, the film thickness E in this case represents the 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.

  The photosensitive transfer sheet of the present invention may have two or more photosensitive layers. As an example, FIG. 6 shows a cross-sectional view when the photosensitive layer has three layers. FIG. 7 shows a case where a barrier layer is provided between each photosensitive layer, FIG. 8 shows a case where a protective film is provided on the photosensitive layer in FIG. 6, and FIG. 7 shows a case where a protective film 56 is provided on the photosensitive layer in FIG. As shown in FIG.

  In the photosensitive transfer sheet 50 of FIGS. 6 to 9, the support is represented by 51, on which the first photosensitive layer 52, the second photosensitive layer 54, and the third photosensitive layer. 55 are sequentially stacked. In the photosensitive transfer sheet 50 of FIG. 7, a barrier layer 53 is provided 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. ing. 8 shows a configuration in which the protective film 56 is provided on the photosensitive transfer sheet of FIG. 6, and FIG. 9 shows a configuration in which the protective film 56 is provided on the photosensitive transfer sheet of FIG.

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

  Using the photosensitive transfer sheet having the configuration shown in FIGS. 6 to 9, the amount of light energy used for pattern formation is set to a light energy amount X for curing only the third photosensitive layer, and the third photosensitive layer. By changing the amount of light energy Y for curing the second photosensitive layer, the amount of light energy Z for curing all of the third photosensitive layer, the second photosensitive layer, and the first photosensitive layer, and the amount of light irradiation. As shown in FIG. 10, on the substrate 57, only the third photosensitive layer 55 has a cured thickness, and the third photosensitive layer 55 and the second photosensitive layer 54 have a cured thickness. A pattern having three different thicknesses, that is, a region having a cured thickness of the region, the third photosensitive layer 55, the second photosensitive layer 54, and the first photosensitive layer 52, is formed by one type of photosensitive transfer sheet. It becomes possible to do.

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

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

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

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

The first photosensitive layer comprising a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator on a support of the present invention, and a photosensitivity containing a binder, a polymerizable compound, and a photopolymerization initiator. A photosensitive transfer sheet comprising a resin composition and a second photosensitive layer having a higher photosensitivity than the first photosensitive layer and laminated in this order, or a first photosensitive layer and a second photosensitive layer, In the case where an image pattern (cured resin pattern) is formed using a photosensitive transfer sheet in which a barrier layer is disposed between, a light energy amount S at which curing of the second photosensitive layer starts is 0.05 to 10 mJ / cm. it is preferably in the ² range, still preferably in the range of 0.1~5mJ / cm ^2, preferably in the range particularly 0.15~2.5mJ / cm ^2. The amount of light energy A necessary for curing the second photosensitive layer is preferably in the range of 0.1~20mJ / cm ^2, that further the range of 0.2~15mJ / cm ² preferably In particular, the range of 0.4 to 10 mJ / cm ² is preferable.

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

[Support]
The support is not particularly limited as long as the light transmittance measured at a wavelength of 405 nm is 80% or more, or the light transmittance measured at a wavelength of 355 nm is 80% or more, and is appropriately selected according to the purpose. Can do. The support having a light transmittance of 80% or more measured at a wavelength of 405 nm preferably has a haze of 11% or less measured at a wavelength of 405 nm. The support having a light transmittance of 80% or more measured at a wavelength of 355 nm preferably has a haze of 11% or less measured at a wavelength of 355 nm.
The support whose light transmittance measured at a wavelength of 405 nm is 80% or more or whose light transmittance measured at a wavelength of 355 nm is 80% or more is high in the wavelength range of 350 to 450 nm, particularly in the range of 355 to 410 nm. The transmittance is shown. For this reason, the high light transmittance is shown with respect to various laser beams.

As the support having a light transmittance of 80% or more measured at the wavelength of 405 nm, for example, the light transmittance is preferably 85% or more, more preferably 87% or more, and further preferably 90% or more.
As a support having a light transmittance of 80% or more measured at the wavelength of 355 nm, for example, the light transmittance is preferably 85% or more, and more preferably 87% or more.
When the light transmittance is less than 80%, the light energy reaching the photosensitive layer decreases, the exposure amount becomes insufficient, the light scattering inside the support increases, and the resolution decreases. There are things to do.

As the support having a light transmittance measured at a wavelength of 405 nm of 80% or more and a support having a haze of 11% or less measured at a wavelength of 405 nm, the haze is preferably 10% or less, more preferably 7% or less. 5% or less is particularly preferable.
As a support having a light transmittance measured at a wavelength of 355 nm of 80% or more and a support having a haze of 11% or less measured at a wavelength of 355 nm, the haze is preferably 10% or less, and more preferably 7% or less. 5% or less is particularly preferable.
When the haze exceeds 11%, light scattering in the photosensitive layer increases, resolution may deteriorate, and the resist shape may be inferior.

Examples of support materials include polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly (meth) acrylic acid ester copolymer, polychlorinated Synthetic resins such as vinyl, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide (nylon), polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, and cellulose Can be mentioned. Furthermore, a composite material composed of two or more of these can also be used.
Among these synthetic resins, polyethylene terephthalate, polyvinyl chloride, and polyimide are preferable, and polyethylene terephthalate is particularly preferable. The thickness of the support is preferably 2 to 150 μm, more preferably 5 to 100 μm, and particularly preferably 8 to 50 μm. The support is preferably a long support. The length of the long support used for producing the photosensitive transfer sheet of the present invention may be arbitrarily determined, and for example, a length of 10 m to 20000 m can be used.

  The support may be surface-treated in order to increase the adhesive force with the first photosensitive layer. Examples of the surface treatment include application of an undercoat layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment. Examples of the material for the undercoat layer include polymers such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, and polyvinyl alcohol. The undercoat layer can be formed by coating the polymer coating solution on the surface of the support and then drying at 30 to 150 ° C. (especially 50 to 120 ° C.) for 1 to 30 minutes.

[Protective film]
Examples of the material for the protective film include those used for the support and paper, or paper laminated with polyethylene or polypropylene. The material of the protective film is preferably polypropylene, polyethylene, cellophane, polypropylene, or polyethylene terephthalate, and particularly preferably polyethylene or polypropylene. 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. The protective film may be surface-treated in order to adjust the adhesiveness with the second photosensitive layer. The example of surface treatment is the same as that of the said support body.

[Combination of support and protective film]
The support and the protective film may be combined such that the adhesive force A between the first photosensitive layer and the support is larger than the adhesive force B between the protective film and the second photosensitive layer (adhesive force A> adhesive force B). preferable. Preferable combinations (support / protective film) of materials for the support and protective film include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. be able to. Moreover, the relationship of the above adhesive forces can be satisfy | filled by processing the surface of at least one of a support body and a protective film.
The coefficient of static friction between the support and the protective film is also important. The static friction coefficient between the support and the protective film is preferably in the range of 0.3 to 1.4, particularly preferably in the range of 0.5 to 1.2. If it is less than 0.3, it slips too much, so that when it is made into a roll, a winding deviation occurs. Moreover, when it exceeds 1.4, it will become difficult to wind in a favorable roll shape.

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

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

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

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

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

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

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

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

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

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

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

  Further, 2-acrylamido-2-methylpropanesulfonic acid, 2-hydroxyethyl acryloyl phosphate, 2-hydroxypropyl acryloyl phosphate, and the like can be used.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  In addition, allyl esters (for example, diallyl phthalate, diallyl adipate, diallyl malonate, diallyl phthalate, triallyl trimellitic acid, diallyl benzenedisulfonate, triallyl isocyanurate); and diallylamide can also be used.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[Barrier layer]
In the photosensitive transfer sheet or 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 suppressing migration of substances contained in the photosensitive layer, support, and protective film, and preventing and suppressing external influences such as oxygen and humidity. For example, the installation of the barrier layer has an effect of preventing the sensitivity and film physical properties from changing due to the components of each photosensitive layer moving to another layer.

  The barrier layer preferably contains a resin, and preferably contains a resin having an affinity for water or a lower alcohol having 1 to 4 carbon atoms as a main component. The affinity means that the solvent has emulsification, dispersion, swelling, partial dissolution, and wettability. Moreover, it is preferable that a barrier layer contains resin soluble as a main component with respect to water or a C1-C4 lower alcohol.

  In the production of the barrier layer, a binder similar to that for the photosensitive layer may be used, but a layer made of a different binder is preferable. Examples of such a polymer include various alcohol-soluble, water-soluble polymers, alcohol-dispersible, water-dispersible, emulsifiable or alkali-soluble polymers, such as polyvinyl alcohol (including modified polyvinyl alcohols), polyvinyl pyrrolidone, Examples thereof include water-soluble polyamide, gelatin, cellulose, and derivatives thereof. These polymers may be used alone or in combination of two or more. Furthermore, various polymers such as an acrylic polymer, an amide polymer, and an ester polymer may be added as long as water solubility and alkali water solubility are not impaired. For the barrier layer, the thermoplastic resin described in Japanese Patent No. 2794242 and compounds used in the intermediate layer can also be used.

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

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

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

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

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

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

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

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

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

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

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

Laser light is preferably used for light irradiation in the step (2). The wavelength of the laser light is preferably in the range of 350 to 450 nm.
Lasers that can be advantageously used for exposure of the photosensitive transfer sheet of the present invention include gallium nitride (GaN) semiconductor lasers (wavelength: 350 to 450 nm), excimer lasers (particularly, XeF lasers, wavelength 351 nm), Nd- YAG laser (third harmonic (THG), wavelength: 355 nm), He-Cd laser (wavelength: 441.6 nm), Ar laser (using mirror for ultraviolet, wavelengths: 351.1 nm, 363.8 nm), Kr laser ( Wavelength: 356.4 nm). If the light transmittance at a wavelength of 405 nm of the support is 90% or more, a gallium nitride (GaN) semiconductor laser (particularly, a wavelength of 405 nm) and a He—Cd laser can be advantageously used. On the other hand, when the light transmittance at a wavelength of 355 nm of the support is 87% or more, an excimer laser, an Nd-YAG laser, an Ar laser, or a Kr laser can be advantageously used.

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

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

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

  As the light source for light irradiation in the step (2), the same light source as in the image pattern forming method is used.

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

  Next, the manufacturing method of the printed wiring board which has a through hole using the photosensitive transfer sheet of this invention is demonstrated, referring FIG. 11 of an accompanying drawing. FIG. 11 shows the case where the photosensitive transfer sheet shown in FIG. 2 or the photosensitive transfer sheet shown in FIG. 4 is used. Even when the photosensitive transfer sheet shown in FIG. 1 or 3 is used, This is the same except that the barrier layer 13 is not included.

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

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

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

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

  Next, as shown in FIG. 11D, the support 11 is peeled off from the laminate (support peeling process).

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

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

  Next, as shown in FIG. 11F, the exposed metal plating layer 23 on the substrate surface is dissolved and removed with an etching solution (etching step). Since the opening of the through hole 22 is covered with the cured resin composition (tent film) 17, the metal plating of the through hole is performed without the etching solution entering the through hole and corroding the metal plating in the through hole. It will remain in a predetermined shape. Thus, the wiring pattern 24 is formed on the printed wiring board forming substrate 21. When the metal plating layer 23 is made of copper, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, a hydrogen peroxide-based etching solution, or the like can be used as the etching solution. Among these, a ferric chloride solution is particularly preferable from the viewpoint of etching factor.

  Next, as shown in FIG. 11G, the hardened layers 16 and 17 are removed from the printed wiring board forming substrate as a release piece 18 with a strong alkaline aqueous solution or the like (hardened product removing step). Examples of the basic component of the strong alkaline aqueous solution include sodium hydroxide and potassium hydroxide. The pH of the strong alkaline aqueous solution used is preferably about 12 to 14, particularly about 13 to 14. Specifically, 1-10 mass% sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, etc. can be used.

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

In this example, 405 nm and 355 nm of a polyethylene terephthalate film (support A, support B, support C, support D, support E, support F, support G, support H) used for the support. Table 1 shows the light transmittance (%) and haze (%) of each wavelength. In addition, light transmittance (%) is the total light transmission with respect to the light of each wavelength using the automatic spectrophotometer (UV-2400, Shimadzu Corporation Corp.) which attached the large integrating sphere attachment apparatus with a diameter of 150 mm. It is a value obtained as a rate. The haze (%) is obtained by the following formula from the parallel light transmittance measured using an automatic spectrophotometer (without using a large integrating sphere attachment device) and the above light transmittance (total light transmittance). Value.
Haze (%) = [light transmittance (total light transmittance) −parallel light transmittance] / light transmittance × 100

Table 1
────────────────────────────────────────
Light transmittance (%) Haze (%)
────────────── ──────────────
405 nm 355 nm 405 nm 355 nm
────────────────────────────────────────
Support A 93.8 90.9 8.2 7.2
Support B 90.0 88.9 2.9 3.1
Support C 92.6 87.3 7.7 5.7
Support D 93.4 88.5 8.7 7.1
Support E 86.7 86.0 3.1 2.8
Support F 87.5 84.8 5.0 6.1
Support G 89.8 88.7 2.9 2.9
Support H 88.4 86.1 4.6 4.9
────────────────────────────────────────
Support A: manufactured by Toyobo Co., Ltd., A4100, thickness 25 μm
Support B: manufactured by Toyobo Co., Ltd., A1517, thickness 16 μm
Support C: Toray Industries, Inc., 25QT32, thickness 25 μm
Support D: Toray Industries, Inc., 16QT38, thickness 16 μm
Support E: Toray Industries, Inc., 16QS52, thickness 16 μm
Support F: Toray Industries, Inc., 16FB50, thickness 16 μm
Support G: Mitsubishi Chemical Polyester Co., Ltd., R340G16, thickness 16 μm
Support H: Mitsubishi Chemical Polyester Co., Ltd., R310-16, thickness 16 μm

[Example 1]
A first photosensitive resin composition solution having the following composition was applied to the support A and dried to form a photosensitive layer (first photosensitive layer) having a thickness of 25 μm.

[Composition of first photosensitive resin composition solution]
────────────────────────────────────────
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymer composition (molar ratio): 55 / 11.7 / 4.5 / 28.8, mass average molecular weight: 90000, Tg : 70 ° C) 15 parts by mass · dodeca polypropylene glycol diacrylate 6.5 parts by mass · tetraethylene glycol dimethacrylate 1.5 parts by mass · 4,4'-bis (diethylamino) benzophenone 0.04 parts by mass · benzophenone 1.0 4 parts by mass, 4-toluenesulfonamide 0.5 parts by mass, malachite green oxalate 0.02 parts by mass, 1,2,4-triazole 0.01 parts by mass, leucocrystal violet 0.2 parts by mass, tribromomethyl 0.1 parts by weight of phenylsulfone, 30 parts by weight of methyl ethyl ketone ─────────────────────────────────────

  Next, a water-soluble polymer solution having the following composition was applied on the first photosensitive layer and dried to form a 1.6 μm thick barrier layer.

[Composition of water-soluble polymer solution]
────────────────────────────────────────
・ Polyvinyl alcohol (PVA205 Kuraray Co., Ltd.) 13 parts by mass ・ Polyvinylpyrrolidone 6 parts by mass ・ Water 200 parts by mass ・ Methanol 180 parts by mass──────────────────── ────────────────────

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

[Composition of second photosensitive resin composition solution]
────────────────────────────────────────
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymer composition (molar ratio): 40 / 26.7 / 4.5 / 28.8, mass average molecular weight: 90000, Tg : 50 ° C) 15 parts by mass-Polypropylene glycol diacrylate 6.5 parts by mass-Tetraethylene glycol dimethacrylate 1.5 parts by mass-4,4'-bis (diethylamino) benzophenone 0.4 parts by mass-Benzophenone 3.0 parts by mass Parts · 4-toluenesulfonamide 0.5 parts by weight · malachite green oxalate 0.02 parts by weight · 1,2,4-triazole 0.01 parts by weight · leuco crystal violet 0.2 parts by weight · tribromomethylphenyl Sulfone 0.1 parts by mass, methyl ethyl ketone 10 parts by mass, 1-methoxy -2-propanol 20 parts by ────────────────────────────────────────

Finally, a 12 μm thick polypropylene film was laminated on the second photosensitive layer to obtain a photosensitive transfer sheet. Next, the above-mentioned photosensitive transfer sheet was wound around the core with a width of 550 mm and a length of 200 m, and a take-up roll was obtained so that the support side became the outside. When the sensitivity of the photosensitive transfer sheet thus obtained was measured by the method described later, the shortest development time was 30 seconds, 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 one photosensitive layer is 40 mJ / cm ² , and the amount of light energy C required for the first photosensitive layer to cure is 14 mJ / cm ² (light energy amount C and light The ratio C / A with the energy amount A was 3.5, and the ratio A / B between the light energy amount A and the light energy amount B was 0.1). When the photosensitivity of the first photosensitive layer was 1, the photosensitivity of the second photosensitive layer was 10.

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

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

[Examples 2 to 8]
A photosensitive transfer sheet was obtained in the same manner as in Example 1 except that the support A was changed as shown in Table 2 below. For the photosensitive transfer sheets obtained in Examples 2 to 8, the shortest development time and sensitivity were measured in the same manner as in Example 1. As a result, the shortest development time and sensitivity were the same as those of the photosensitive transfer sheet obtained in Example 1.

[Evaluation]
About the photosensitive transfer sheet obtained in Examples 1-8, the resolution and adhesiveness with respect to the laser beam of wavelength 405nm and wavelength 355nm were measured with the following method. The results are shown in Table 2. Note that the laser light irradiation condition of wavelength 405 nm was 30 mW output, GaN-based semiconductor laser, CW oscillation, and beam diameter (half value) 9 μmφ. The irradiation conditions of the laser light with a wavelength of 355 nm were an output of 4 mW, an Nd-YAG laser, a third harmonic (THG), a pseudo continuous oscillation (80 MHz pulse oscillation), and a beam diameter (half value) of 12 μmφ.

[Measurement method of resolution]
A copper-clad laminate, a second photosensitive layer, a barrier layer, a first photosensitive layer, and a polyethylene terephthalate film were laminated in this order under the same conditions as the evaluation method for the shortest development time of (1) in the sensitivity measurement method. A laminate is prepared and allowed to stand at room temperature (23 ° C., 55% RH) for 10 minutes. From the obtained polyethylene terephthalate film of the laminate, exposure is performed by irradiating a laser beam having a wavelength of 405 nm and a wavelength of 355 nm with a line / space = 1/1 pattern having a line width of 10 μm to 50 μm in increments of 5 μm. The exposure amount at this time is the amount of light energy that cures the second photosensitive layer of each photosensitive transfer sheet. After leaving still at room temperature for 10 minutes, a polyethylene terephthalate film is peeled off from a laminated body. An uncured resin is sprayed on the entire surface of the resin composition layer on the copper-clad laminate by spraying a 1% by mass sodium carbonate aqueous solution at 30 ° C. at a spray pressure of 0.15 MPa for twice the shortest development time obtained above. Dissolve the composition. The surface of the copper-clad laminate with the cured resin pattern thus obtained was observed with an optical microscope, and the minimum line width without any abnormalities such as tsumari and twisting was measured on the cured resin pattern line. To do. The smaller the numerical value, the better the resolution.

[Measurement method of adhesion]
Except for irradiating the laser beam in a pattern of 5 μm increments from line / space = 1/3 and line width of 10 μm to 100 μm, the same operation as the resolution measurement method was performed, and the cured resin pattern was peeled off the line, causing abnormalities such as twisting Measure the smallest minimum line width and use this as the contact. The smaller the numerical value, the better the adhesion.

Table 2
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Laser light with a wavelength of 405 nm Laser light with a wavelength of 355 nm
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Support Resolution Resolution Adhesion Resolution Adhesion ────────────────────────────────────────
Example 1 Support A 20 μm 15 μm 20 μm 15 μm
Example 2 Support B 20 μm 15 μm 20 μm 15 μm
Example 3 Support C 20 μm 15 μm 20 μm 15 μm
Example 4 Support D 20 μm 15 μm 20 μm 15 μm
Example 5 Support E 20 μm 15 μm 20 μm 15 μm
Example 6 Support F 20 μm 15 μm 20 μm 15 μm
Example 7 Support G 20 μm 15 μm 20 μm 15 μm
Example 8 Support H 20 μm 15 μm 20 μm 15 μm
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It is a schematic cross section of an example of the photosensitive transfer sheet according to the present invention. It is a schematic cross section of the other example of the photosensitive transfer sheet according to the present invention. It is a schematic cross section of the other example of the photosensitive transfer sheet according to the present invention. It is a schematic cross section of the other example of the photosensitive transfer sheet according to the present invention. It is a graph which shows the sensitivity curve showing the relationship between the irradiation amount of light, and the thickness of a hardening layer when light is irradiated to the photosensitive transfer sheet of this invention from the support body side. It is a schematic cross section of an example of the photosensitive transfer sheet according to the present invention. It is a schematic cross section of the other example of the photosensitive transfer sheet according to the present invention. It is a schematic cross section of the other example of the photosensitive transfer sheet according to the present invention. It is a schematic cross section of the other example of the photosensitive transfer sheet according to the present invention. It is a schematic diagram which shows the example of an image (hardened layer pattern) which can be formed using the photosensitive transfer sheet whose photosensitive layer according to this invention is three layers. It is process drawing which shows the manufacturing process of the printed wiring board which has a through hole according to this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Photosensitive transfer sheet 11 Support body 12 1st photosensitive layer 13 Barrier layer 14 2nd photosensitive layer 15 Protective film 16 Hardened layer for wiring pattern formation 17 Hardened layer for metal layer protection of a through hole 18 Peeling piece 21 Printed wiring board formation Substrate 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

Claims (37)

  A first photosensitive layer comprising a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator on a support having a light transmittance of 80% or more measured at a wavelength of 405 nm, and a binder and a polymerizable compound And a photosensitive transfer composition comprising a photosensitive resin composition containing a photopolymerization initiator, wherein a second photosensitive layer having a higher photosensitivity than the first photosensitive layer is laminated in this order.   The photosensitive transfer sheet according to claim 1, wherein the support has a haze measured at a wavelength of 405 nm of 11% or less.   A first photosensitive layer comprising a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator on a support having a light transmittance of 80% or more measured at a wavelength of 355 nm, and a binder and a polymerizable compound And a photosensitive transfer composition comprising a photosensitive resin composition containing a photopolymerization initiator, wherein a second photosensitive layer having a higher photosensitivity than the first photosensitive layer is laminated in this order.   The photosensitive transfer sheet according to claim 3, wherein the support has a haze measured at a wavelength of 355 nm of 11% or less.   The photosensitive transfer sheet according to any one of claims 1 to 4, wherein a barrier layer is disposed between the first photosensitive layer and the second photosensitive layer.   The photosensitive transfer sheet according to claim 5, wherein the barrier layer contains, as a main component, water or a resin having an affinity for a lower alcohol having 1 to 4 carbon atoms.   The photosensitive transfer sheet according to claim 5 or 6, wherein the barrier layer contains, as a main component, a resin that is soluble in water or a lower alcohol having 1 to 4 carbon atoms.   The photosensitive transfer sheet according to claim 5, wherein the barrier layer has a thickness in the range of 0.1 to 5 μm.   The photosensitive transfer sheet according to any one of claims 1 to 8, wherein the photosensitivity of the first photosensitive layer is 1 and the photosensitivity of the second photosensitive layer is in the range of 2 to 200.   The ratio expressed by A / B between the amount of light energy A required to cure the second photosensitive layer and the amount of light energy B necessary to cure the first photosensitive layer is 0.005 to 0.5. The photosensitive transfer sheet according to any one of claims 1 to 9, which is in the range of.   The ratio represented by C / A between the amount of light energy A required to cure the second photosensitive layer and the amount of light energy C required until the first photosensitive layer begins to be cured is in the range of 1-10. The photosensitive transfer sheet according to any one of claims 1 to 10.   The photosensitive transfer sheet according to any one of claims 1 to 11, wherein each of the first photosensitive layer and the second photosensitive layer contains a sensitizer.   The photosensitive transfer sheet according to claim 12, wherein the amount of the sensitizer contained in the second photosensitive layer is larger than the amount of the sensitizer contained in the first photosensitive layer.   The photosensitivity according to any one of claims 1 to 13, wherein the amount of the photopolymerization initiator contained in the second photosensitive layer is larger than the amount of the photopolymerization initiator contained in the first photosensitive layer. Transfer sheet.   The photosensitive transfer according to any one of claims 1 to 14, wherein the amount of the polymerizable compound contained in the second photosensitive layer is larger than the amount of the polymerizable compound contained in the first photosensitive layer. Sheet.   The photosensitive transfer sheet according to any one of claims 1 to 15, wherein the first photosensitive layer has a thickness in the range of 1 to 100 µm, and the thickness is larger than the thickness of the second photosensitive layer.   The photosensitive transfer sheet according to any one of claims 1 to 16, wherein the second photosensitive layer has a thickness in the range of 0.1 to 15 µm.   The photosensitive transfer sheet according to any one of claims 1 to 17, wherein the support is made of a synthetic resin.   Synthetic resin is polyethylene terephthalate, polyethylene naphthalate, polyethylene, cellulose triacetate, cellulose diacetate, cellulose, polyacrylate ester, polymethacrylate ester, polyvinyl chloride, polyamide, polyimide, polyvinyl acetate, polytetrafluoroethylene, The photosensitive transfer sheet according to claim 18, which is selected from the group consisting of polytrifluoroethylene and copolymers thereof.   The photosensitive transfer sheet according to any one of claims 1 to 19, wherein the support is a long support.   The photosensitive transfer sheet according to any one of claims 1 to 20, wherein a protective film is disposed on the second photosensitive layer.   The photosensitive transfer sheet according to any one of claims 1 to 21, which is a long body and is wound in a roll shape.   The photosensitive transfer sheet according to any one of claims 1 to 22, which is used for producing a printed wiring board.   The substrate comprises a second photosensitive layer comprising a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator, and a photosensitive resin composition comprising a binder, a polymerizable compound, and a photopolymerization initiator. A photosensitive laminate in which a first photosensitive layer having a light sensitivity relatively lower than that of the second photosensitive layer and a support having a light transmittance of 80% or more measured at a wavelength of 405 nm are laminated in this order. .   The photosensitive laminate according to claim 24, wherein the support has a haze of 11% or less measured at a wavelength of 405 nm.   The substrate comprises a second photosensitive layer comprising a photosensitive resin composition containing a binder, a polymerizable compound, and a photopolymerization initiator, and a photosensitive resin composition comprising a binder, a polymerizable compound, and a photopolymerization initiator. A photosensitive laminate in which a first photosensitive layer having a light sensitivity relatively lower than that of the second photosensitive layer and a support having a light transmittance of 80% or more measured at a wavelength of 355 nm are laminated in this order. .   27. The photosensitive laminate according to claim 26, wherein the support has a haze of 11% or less measured at a wavelength of 355 nm.   28. The photosensitive laminate according to any one of claims 24 to 27, wherein a barrier layer is disposed between the first photosensitive layer and the second photosensitive layer.   The photosensitive laminate according to claim 28, wherein the barrier layer contains, as a main component, a resin having an affinity for water or a lower alcohol having 1 to 4 carbon atoms.   30. The photosensitive laminate according to claim 28 or 29, wherein the barrier layer contains, as a main component, a resin that is soluble in water or a lower alcohol having 1 to 4 carbon atoms.   The photosensitive laminate according to any one of claims 28 to 30, wherein the substrate is a printed wiring board forming substrate. An image comprising a region where a cured resin layer formed by curing both the first photosensitive layer and the second photosensitive layer on a substrate and a region where no cured resin layer is present, including the following steps: How to form a pattern:
(1) A step of obtaining a laminate by laminating the photosensitive transfer sheet according to any one of claims 1 to 4 on a substrate in a positional relationship in which the second photosensitive layer is on the substrate side. ;
(2) A step of performing light irradiation of a predetermined image pattern from the side of the first photosensitive layer of the laminate and curing both the first photosensitive layer and the second photosensitive layer in the region irradiated with the light;
(3) removing the support from the laminate; and
(4) The process of developing a laminated body and removing the unhardened part in a laminated body. A region including a resin layer formed by curing the first photosensitive layer and the second photosensitive layer on the substrate, including the following steps: a resin layer formed by curing the second photosensitive layer A method of forming an image pattern composed of a region in which a cured resin layer does not exist:
(1) A step of obtaining a laminate by laminating the photosensitive transfer sheet according to any one of claims 1 to 4 on a substrate in a positional relationship in which the second photosensitive layer is on the substrate side. ;
(2) Light irradiation is performed from the first photosensitive layer side of the laminate with an image pattern that defines a region to be irradiated with at least two different levels of irradiation energy amount, and the light irradiation energy amount is relatively large Curing both the first photosensitive layer and the second photosensitive layer in the region irradiated with light, and curing the second photosensitive layer in the region irradiated with light having a relatively small amount of light irradiation energy;
(3) removing the support from the laminate; and
(4) The process of developing a laminated body and removing the unhardened part in a laminated body.   The method according to claim 32 or 33, wherein the light irradiation in the step (2) is performed by laser light irradiation. The area covered with the cured resin layer formed by curing the first photosensitive layer and the second photosensitive layer on the printed wiring board forming substrate including the following steps and the substrate surface are exposed. A method of forming a wiring pattern composed of a region including:
(1) A step of obtaining a laminate by laminating the photosensitive transfer sheet according to any one of claims 1 to 4 on a substrate in a positional relationship in which the second photosensitive layer is on the substrate side. ;
(2) A step of irradiating a predetermined wiring pattern from the first photosensitive layer side of the laminate and curing both the first photosensitive layer and the second photosensitive layer in the irradiated region;
(3) removing the support from the laminate; and
(4) The process of developing a laminated body and removing the unhardened part in a laminated body. A hole part covered with a cured resin layer formed by curing both the first photosensitive layer and the second photosensitive layer on a printed wiring board forming substrate having a hole part, including the following steps: A method of forming a wiring pattern composed of a region covered with a cured resin layer formed by curing a photosensitive layer and a region where a substrate surface is exposed:
(1) A step of obtaining a laminate by laminating the photosensitive transfer sheet according to any one of claims 1 to 4 on a substrate in a positional relationship in which the second photosensitive layer is on the substrate side. ;
(2) From the side of the first photosensitive layer of the laminate, the hole portion is irradiated with light having a relatively large amount of light irradiation energy to cure both the first photosensitive layer and the second photosensitive layer, and wiring A step of irradiating the formation region with light of an image pattern that cures the second photosensitive layer by applying light irradiation with a relatively small amount of light irradiation energy;
(3) removing the support from the laminate; and
(4) The process of developing a laminated body and removing the unhardened part in a laminated body.   The method according to claim 35 or 36, wherein the light irradiation in the step (2) is performed by laser light irradiation.

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